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Metal nitrosyl complex

February 08, 2023

Not to be confused with Nitro compound.

Metal nitrosyl complexes are complexes that contain nitric oxide, NO, bonded to a transition metal.[2] Many kinds of nitrosyl complexes are known, which vary both in structure and coligand.

Sodium nitroprusside, a medicinally significant metal nitrosyl-pentacyanoferrate (Fe-III) compound, used to treat hypertension.[1]

Bonding and structure

 
(Top) the HOMO and LUMO of CO. (Middle) Sigma bond. (Bottom) Back-bond.

Most complexes containing the NO ligand can be viewed as derivatives of the nitrosyl cation, NO+. The nitrosyl cation is isoelectronic with carbon monoxide, thus the bonding between a nitrosyl ligand and a metal follows the same principles as the bonding in carbonyl complexes. The nitrosyl cation serves as a two-electron donor to the metal and accepts electrons from the metal via back-bonding. The compounds Co(NO)(CO)3 and Ni(CO)4 illustrate the analogy between NO+ and CO. In an electron-counting sense, two linear NO ligands are equivalent to three CO groups. This trend is illustrated by the isoelectronic pair Fe(CO)2(NO)2 and [Ni(CO)4].[3] These complexes are isoelectronic and, incidentally, both obey the 18-electron rule. The formal description of nitric oxide as NO+ does not match certain measureable and calculated properties. In an alternative description, nitric oxide serves as a 3-electron donor, and the metal-nitrogen interaction is a triple bond.

 
linear and bent M-NO bonds

Linear vs bent nitrosyl ligands

The M-N-O unit in nitrosyl complexes is usually linear, or no more than 15° from linear. In some complexes, however, especially when back-bonding is less important, the M-N-O angle can strongly deviate from 180°. Linear and bent NO ligands can be distinguished using infrared spectroscopy. Linear M-N-O groups absorb in the range 1650–1900 cm−1, whereas bent nitrosyls absorb in the range 1525–1690 cm−1. The differing vibrational frequencies reflect the differing N-O bond orders for linear (triple bond) and bent NO (double bond).

The bent NO ligand is sometimes described as the anion, NO−. Prototypes for such compounds are the organic nitroso compounds, such as nitrosobenzene. A complex with a bent NO ligand is trans-[Co(en)2(NO)Cl]+. The NO− is also common for alkali-metal or alkaline-earth metal-NO molecules. For example. LiNO and BeNO bear Li+NO− and Be+NO− ionic form.[4][5]

The adoption of linear vs bent bonding can be analyzed with the Enemark-Feltham notation.[6] In their framework, the factor that determines the bent vs linear NO ligands is the sum of electrons of pi-symmetry. Complexes with "pi-electrons" in excess of 6 tend to have bent NO ligands. Thus, [Co(en)2(NO)Cl]+, with eight electrons of pi-symmetry (six in t2g orbitals and two on NO, {CoNO}8), adopts a bent NO ligand, whereas [Fe(CN)5(NO)]2−, with six electrons of pi-symmetry, {FeNO}6), adopts a linear nitrosyl. In a further illustration, the {MNO} d-electron count of the [Cr(CN)5NO]3− anion is shown. In this example, the cyanide ligands are "innocent", i.e., they have a charge of −1 each, −5 total. To balance the fragment's overall charge, the charge on {CrNO} is thus +2 (−3 = −5 + 2). Using the neutral electron counting scheme, Cr has 6 d electrons and NO· has one electron for a total of 7. Two electrons are subtracted to take into account that fragment's overall charge of +2, to give 5. Written in the Enemark-Feltham notation, the d electron count is {CrNO}5. The results are the same if the nitrosyl ligand were considered NO+ or NO−.[6]

Bridging nitrosyl ligands

Nitric oxide can also serve as a bridging ligand. In the compound [Mn3(η5C5H5)3 (μ2-NO)3 (μ3-NO)], three NO groups bridge two metal centres and one NO group bridge to all three.[3]

Isonitrosyl ligands

 
Structure of the isonitrosyl complex [Ru(Cl)(ON)(pyridine)4]+ (color code: red (O), blue (N), gray (C), dark green (Ru), green (Cl)).

Usually only of transient existence, complexes of isonitrosyl ligands are known where the NO is coordinated by its oxygen atom. They can be generated by UV-irradiation of nitrosyl complexes.[7]

Representative classes of compounds

Homoleptic nitrosyl complexes

Metal complexes containing only nitrosyl ligands are called isoleptic nitrosyls. They are rare, the premier member being Cr(NO)4.[8] Even trinitrosyl complexes are uncommon, whereas polycarbonyl complexes are routine.

Roussin red and black salts

One of the earliest examples of a nitrosyl complex to be synthesized is Roussin's red salt, which is a sodium salt of the anion [Fe2(NO)4S2]2−. The structure of the anion can be viewed as consisting of two tetrahedra sharing an edge. Each iron atom is bonded linearly to two NO+ ligands and shares two bridging sulfido ligands with the other iron atom. Roussin's black salt has a more complex cluster structure. The anion in this species has the formula [Fe4(NO)7S3]−. It has C3v symmetry. It consists of a tetrahedron of iron atoms with sulfide ions on three faces of the tetrahedron. Three iron atoms are bonded to two nitrosyl groups. The iron atom on the threefold symmetry axis has a single nitrosyl group which also lies on that axis.

  •  

    The anion in Roussin's red salt, [Fe2S2(NO)4]2−.

  •  

    The anion in Roussin's black salt, [Fe4S3(NO)7]−.

  •  

    The nitroprusside anion, [Fe(CN)5NO]2−, an octahedral complex containing a "linear NO" ligand.

  •  

    trans-[Co(en)2(NO)Cl]+, an octahedral complex containing a "bent NO" ligand.

Preparation

Many nitrosyl complexes are quite stable, thus many methods can be used for their synthesis.[9]

From NO

Nitrosyl complexes are traditionally prepared by treating metal complexes with nitric oxide. The method is mainly used with reduced precursors. Illustrative is the nitrosylation of cobalt carbonyl to give cobalt tricarbonyl nitrosyl:[10]

Co2(CO)8 + 2 NO → 2 CoNO(CO)3 + 2 CO

From NO+ and NOCl

Replacement of ligands by the nitrosyl cation may be accomplished using nitrosyl tetrafluoroborate. This reagent has been applied to the hexacarbonyls of molybdenum and tungsten:[11][12]

M(CO)6 + 4 MeCN + 2 NOBF4 → [M(NO)2(MeCN)4](BF4)2

Nitrosyl chloride and molybdenum hexacarbonyl react to give [Mo(NO)2Cl2]n.[13] Diazald is also used as an NO source.[14]

From hydroxylamine

Hydroxylamine is a source of nitric oxide anion via a disproportionation:

K2[Ni(CN)4] + 2 NH2OH + KOH → K2[Ni(CN)3)NO] + NH3 + 2 H2O + KCN

From nitric acid

Nitric acid is a source of nitric oxide complexes, although the details are obscure. Probably relevant is the conventional self-dehydration of nitric acid:

2 HNO3 → NO2+NO3− + H2O

Nitric acid is used in some preparations of nitroprusside from ferrocyanide:

HNO3 + [Fe(CN)6]4- → [Fe(CN)5(NO)]2- + OH− + OCN−

From nitrous acid

Some anionic nitrito complexes undergo acid-induced deoxygenation to give the linear nitrosyl complex.

[LnMNO2]− + H+ → [LnMNO] + OH−

The reaction is reversible in some cases.

Oxidation of ammine complexes

In some metal-ammine complexes, the ammonia ligand can be oxidized to nitrosyl:[15]

H2O + [Ru(terpy)(bipy)(NH3)]+ → [Ru(terpy)(bipy)(NO)]2+ + 5 H+ + 6 e−

Reactions

An important reaction is the acid/base equilibrium, yielding transition metal nitrite complexes:

[LnMNO]2+ + 2OH− ⇌ LnMNO2 + H2O

This equilibrium serves to confirm that the linear nitrosyl ligand is, formally, NO+, with nitrogen in the oxidation state +3

NO+ + 2 OH− ⇌ NO2− + H2O

Since nitrogen is more electronegative than carbon, metal-nitrosyl complexes tend to be more electrophilic than related metal carbonyl complexes. Nucleophiles often add to the nitrogen.[2] The nitrogen atom in bent metal nitrosyls is basic, thus can be oxidized, alkylated, and protonated, e.g.:

(Ph3P)2(CO)ClOsNO + HCl → (Ph3P)2(CO)ClOsN(H)O

In rare cases, NO is cleaved by metal centers:

Cp2NbMe2 + NO → Cp2(Me)Nb(O)NMe
2 Cp2(Me)Nb(O)NMe → 2 Cp2Nb(O)Me + ½MeN=NMe
 
Nitrosylation of a heme-thiolate, steps in cell signaling by nitric oxide (porphyrin is depicted as the square).[16]

Applications

Metal-nitrosyls are assumed to be intermediates in catalytic converters, which reduce the emission of NOx from internal combustion engines. This application has been described as “one of the most successful stories in the development of catalysts.”[17]

 
Structure of a dinitrosyl iron complex (DNIC).[18]

Metal-catalyzed reactions of NO are not often useful in organic chemistry. In biology and medicine, nitric oxide is however an important signalling molecule in nature and this fact is the basis of the most important applications of metal nitrosyls. The nitroprusside anion, [Fe(CN)5NO]2−, a mixed nitrosyl cyano complex, has pharmaceutical applications as a slow release agent for NO. The signalling function of NO is effected via its complexation to haeme proteins, where it binds in the bent geometry. Nitric oxide also attacks iron-sulfur proteins giving dinitrosyl iron complexes.

Thionitrosyls

Several complexes are known with NS ligands. Like nitrosyls, thionitrosyls exist as both linear and bent geometries.[19]

References

  1. ^ "Sodium Nitroprusside". www.drugs.com. The American Society of Health-System Pharmacists. Retrieved 21 October 2022.
  2. ^ a b Hayton, T. W.; Legzdins, P.; Sharp, W. B. (2002). "Coordination and Organometallic Chemistry of Metal-NO Complexes". Chem. Rev. 102 (1): 935–991. doi:10.1021/cr000074t. PMID 11942784.
  3. ^ a b Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 447–453. ISBN 978-0-08-037941-8.
  4. ^ Ariyarathna, Isuru R.; Miliordos, Evangelos (15 July 2019). "Electronic and geometric structure analysis of neutral and anionic metal nitric chalcogens: The case of MNX series (M=Li, Na, Be and X=O, S, Se, Te)". Journal of Computational Chemistry. 40 (19): 1740–1751. doi:10.1002/jcc.25829. PMID 30920017. S2CID 85546245.
  5. ^ Ariyarathna, Isuru (1 March 2021). "First Principle Studies on Ground and Excited Electronic States: Chemical Bonding in Main-Group Molecules, Molecular Systems with Diffuse Electrons, and Water Activation using Transition Metal Monoxides".
  6. ^ a b Enemark, J. H.; Feltham, R. D. (1974). "Principles of structure, bonding, and reactivity for metal nitrosyl complexes". Coord. Chem. Rev. 1974 (13): 339–406. doi:10.1016/S0010-8545(00)80259-3.
  7. ^ Mikhailov, Artem A.; Wenger, Emmanuel; Kostin, Gennadiy A.; Schaniel, Dominik (2019). "Room‐Temperature Photogeneration of Nitrosyl Linkage Isomers in Ruthenium Nitrosyl Complexes" (PDF). Chemistry – A European Journal. 25 (31): 7569–7574. doi:10.1002/chem.201901205. PMID 30957917. S2CID 102349334.
  8. ^ Herberhold Max (1972). "Tetranitrosylchromium [Cr(NO)4]". Angewandte Chemie International Edition in English. 11 (12): 1092–1094. doi:10.1002/anie.197210921.
  9. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 449. ISBN 978-0-08-037941-8.
  10. ^ Paul Gilmont Arthur A. Blanchard (1946). "Dicobalt Octacarbonyl, Cobalt Nitrosyl Tricarbonyl, and Cobalt Tetracarbomyl Hydride". Inorganic Syntheses. Inorg. Synth. Inorganic Syntheses. Vol. 2. p. 238. doi:10.1002/9780470132333.ch76. ISBN 9780470132333.{{cite book}}: CS1 maint: uses authors parameter (link)
  11. ^ Richard R. Thomas, Ayusman Sen (1990). "Acetonitrile Complexes of Selected Transition Metal Cations". Inorganic Syntheses. Inorg. Synth. Inorganic Syntheses. Vol. 28. pp. 63–67. doi:10.1002/9780470132593.ch14. ISBN 9780470132593.{{cite book}}: CS1 maint: uses authors parameter (link)
  12. ^ Francine Agbossou Edward J. O'Connor Charles M. Garner N. Quirós Méndez Jesús M. Fernández Alan T. Patton James A. Ramsden J. A. Gladysz (1992). "Cyclopentadienyl Rhenium Complexes". Inorganic Syntheses. Inorg. Synth. Inorganic Syntheses. Vol. 29. pp. 211–225. doi:10.1002/9780470132609.ch51. ISBN 9780470132609.{{cite book}}: CS1 maint: uses authors parameter (link)
  13. ^ B. F. G. Johnson K. H. Al‐Obadi (1970). "Dihalogenodinitrosylmolybdenum and Dihalogenodinitrosyltungsten". Inorganic Syntheses. Inorg. Synth. Inorganic Syntheses. Vol. 12. pp. 264–266. doi:10.1002/9780470132432.ch47. ISBN 9780470132432.{{cite book}}: CS1 maint: uses authors parameter (link)
  14. ^ James K. Hoyano, Peter Legzdins, John T. Malito (1978). "(η5-Cyclopentadienydnitrosyl Complexes of Chromium, Molybdenum, and Jungsten". (η5‐Cyclopentadienydnitrosyl Complexes of Chromium, Molybdenum, and Tungsten. Inorg. Synth. Inorganic Syntheses. Vol. 13. pp. 126–131. doi:10.1002/9780470132494.ch21. ISBN 9780470132494.{{cite book}}: CS1 maint: uses authors parameter (link)
  15. ^ Dunn, Peter L.; Cook, Brian J.; Johnson, Samantha I.; Appel, Aaron M.; Bullock, R. Morris (2020). "Oxidation of Ammonia with Molecular Complexes". Journal of the American Chemical Society. 142 (42): 17845–17858. doi:10.1021/jacs.0c08269. OSTI 1706682. PMID 32977718. S2CID 221938378.
  16. ^ Walker, F. A. (2005). "Nitric Oxide Interaction with Insect Nitrophorins and Thoughts on the Electron Configuration of the FeNO6 Complex". J. Inorg. Biochem. 99 (1): 216–236. doi:10.1016/j.jinorgbio.2004.10.009. PMID 15598503.
  17. ^ Kaspar, Jan; Fornasiero, Paolo; Hickey, Neal (2003). "Automotive Catalytic Converters: Current Status and Some Perspectives". Catalysis Today. 77 (4): 419–449. doi:10.1016/S0920-5861(02)00384-X.{{cite journal}}: CS1 maint: uses authors parameter (link)
  18. ^ Jessica Fitzpatrick, Eunsuk Kim (2015). "Synthetic Modeling Chemistry of Iron–Sulfur Clusters in Nitric Oxide Signaling". Acc. Chem. Res. 48 (8): 2453–2461. doi:10.1021/acs.accounts.5b00246. PMID 26197209.{{cite journal}}: CS1 maint: uses authors parameter (link)
  19. ^ Ng, Ho-Yuen; Cheung, Wai-Man; Kwan Huang, Enrique; Wong, Kang-Long; Sung, Herman H.-Y.; Williams, Ian D.; Leung, Wa-Hung (2015). "Ruthenium chalcogenonitrosyl and bridged nitrido complexes containing chelating sulfur and oxygen ligands". Dalton Transactions. 44 (42): 18459–18468. doi:10.1039/C5DT02513C. PMID 26442594.

February 08, 2023
metal, nitrosyl, complex, confused, with, nitro, compound, complexes, that, contain, nitric, oxide, bonded, transition, metal, many, kinds, nitrosyl, complexes, known, which, vary, both, structure, coligand, sodium, nitroprusside, medicinally, significant, met. Not to be confused with Nitro compound Metal nitrosyl complexes are complexes that contain nitric oxide NO bonded to a transition metal 2 Many kinds of nitrosyl complexes are known which vary both in structure and coligand Sodium nitroprusside a medicinally significant metal nitrosyl pentacyanoferrate Fe III compound used to treat hypertension 1 Contents 1 Bonding and structure 1 1 Linear vs bent nitrosyl ligands 1 2 Bridging nitrosyl ligands 1 3 Isonitrosyl ligands 2 Representative classes of compounds 2 1 Homoleptic nitrosyl complexes 2 2 Roussin red and black salts 3 Preparation 3 1 From NO 3 2 From NO and NOCl 3 3 From hydroxylamine 3 4 From nitric acid 3 5 From nitrous acid 3 6 Oxidation of ammine complexes 4 Reactions 5 Applications 6 Thionitrosyls 7 ReferencesBonding and structure Edit Top the HOMO and LUMO of CO Middle Sigma bond Bottom Back bond Most complexes containing the NO ligand can be viewed as derivatives of the nitrosyl cation NO The nitrosyl cation is isoelectronic with carbon monoxide thus the bonding between a nitrosyl ligand and a metal follows the same principles as the bonding in carbonyl complexes The nitrosyl cation serves as a two electron donor to the metal and accepts electrons from the metal via back bonding The compounds Co NO CO 3 and Ni CO 4 illustrate the analogy between NO and CO In an electron counting sense two linear NO ligands are equivalent to three CO groups This trend is illustrated by the isoelectronic pair Fe CO 2 NO 2 and Ni CO 4 3 These complexes are isoelectronic and incidentally both obey the 18 electron rule The formal description of nitric oxide as NO does not match certain measureable and calculated properties In an alternative description nitric oxide serves as a 3 electron donor and the metal nitrogen interaction is a triple bond linear and bent M NO bonds Linear vs bent nitrosyl ligands Edit The M N O unit in nitrosyl complexes is usually linear or no more than 15 from linear In some complexes however especially when back bonding is less important the M N O angle can strongly deviate from 180 Linear and bent NO ligands can be distinguished using infrared spectroscopy Linear M N O groups absorb in the range 1650 1900 cm 1 whereas bent nitrosyls absorb in the range 1525 1690 cm 1 The differing vibrational frequencies reflect the differing N O bond orders for linear triple bond and bent NO double bond The bent NO ligand is sometimes described as the anion NO Prototypes for such compounds are the organic nitroso compounds such as nitrosobenzene A complex with a bent NO ligand is trans Co en 2 NO Cl The NO is also common for alkali metal or alkaline earth metal NO molecules For example LiNO and BeNO bear Li NO and Be NO ionic form 4 5 The adoption of linear vs bent bonding can be analyzed with the Enemark Feltham notation 6 In their framework the factor that determines the bent vs linear NO ligands is the sum of electrons of pi symmetry Complexes with pi electrons in excess of 6 tend to have bent NO ligands Thus Co en 2 NO Cl with eight electrons of pi symmetry six in t2g orbitals and two on NO CoNO 8 adopts a bent NO ligand whereas Fe CN 5 NO 2 with six electrons of pi symmetry FeNO 6 adopts a linear nitrosyl In a further illustration the MNO d electron count of the Cr CN 5NO 3 anion is shown In this example the cyanide ligands are innocent i e they have a charge of 1 each 5 total To balance the fragment s overall charge the charge on CrNO is thus 2 3 5 2 Using the neutral electron counting scheme Cr has 6 d electrons and NO has one electron for a total of 7 Two electrons are subtracted to take into account that fragment s overall charge of 2 to give 5 Written in the Enemark Feltham notation the d electron count is CrNO 5 The results are the same if the nitrosyl ligand were considered NO or NO 6 Bridging nitrosyl ligands Edit Nitric oxide can also serve as a bridging ligand In the compound Mn3 h5C5H5 3 m2 NO 3 m3 NO three NO groups bridge two metal centres and one NO group bridge to all three 3 Isonitrosyl ligands Edit Structure of the isonitrosyl complex Ru Cl ON pyridine 4 color code red O blue N gray C dark green Ru green Cl Usually only of transient existence complexes of isonitrosyl ligands are known where the NO is coordinated by its oxygen atom They can be generated by UV irradiation of nitrosyl complexes 7 Representative classes of compounds EditHomoleptic nitrosyl complexes Edit Metal complexes containing only nitrosyl ligands are called isoleptic nitrosyls They are rare the premier member being Cr NO 4 8 Even trinitrosyl complexes are uncommon whereas polycarbonyl complexes are routine Roussin red and black salts Edit One of the earliest examples of a nitrosyl complex to be synthesized is Roussin s red salt which is a sodium salt of the anion Fe2 NO 4S2 2 The structure of the anion can be viewed as consisting of two tetrahedra sharing an edge Each iron atom is bonded linearly to two NO ligands and shares two bridging sulfido ligands with the other iron atom Roussin s black salt has a more complex cluster structure The anion in this species has the formula Fe4 NO 7S3 It has C3v symmetry It consists of a tetrahedron of iron atoms with sulfide ions on three faces of the tetrahedron Three iron atoms are bonded to two nitrosyl groups The iron atom on the threefold symmetry axis has a single nitrosyl group which also lies on that axis The anion in Roussin s red salt Fe2S2 NO 4 2 The anion in Roussin s black salt Fe4S3 NO 7 The nitroprusside anion Fe CN 5NO 2 an octahedral complex containing a linear NO ligand trans Co en 2 NO Cl an octahedral complex containing a bent NO ligand Preparation EditMany nitrosyl complexes are quite stable thus many methods can be used for their synthesis 9 From NO Edit Nitrosyl complexes are traditionally prepared by treating metal complexes with nitric oxide The method is mainly used with reduced precursors Illustrative is the nitrosylation of cobalt carbonyl to give cobalt tricarbonyl nitrosyl 10 Co2 CO 8 2 NO 2 CoNO CO 3 2 COFrom NO and NOCl Edit Replacement of ligands by the nitrosyl cation may be accomplished using nitrosyl tetrafluoroborate This reagent has been applied to the hexacarbonyls of molybdenum and tungsten 11 12 M CO 6 4 MeCN 2 NOBF4 M NO 2 MeCN 4 BF4 2Nitrosyl chloride and molybdenum hexacarbonyl react to give Mo NO 2Cl2 n 13 Diazald is also used as an NO source 14 From hydroxylamine Edit Hydroxylamine is a source of nitric oxide anion via a disproportionation K2 Ni CN 4 2 NH2OH KOH K2 Ni CN 3 NO NH3 2 H2O KCNFrom nitric acid Edit Nitric acid is a source of nitric oxide complexes although the details are obscure Probably relevant is the conventional self dehydration of nitric acid 2 HNO3 NO2 NO3 H2ONitric acid is used in some preparations of nitroprusside from ferrocyanide HNO3 Fe CN 6 4 Fe CN 5 NO 2 OH OCN From nitrous acid Edit Some anionic nitrito complexes undergo acid induced deoxygenation to give the linear nitrosyl complex LnMNO2 H LnMNO OH The reaction is reversible in some cases Oxidation of ammine complexes Edit In some metal ammine complexes the ammonia ligand can be oxidized to nitrosyl 15 H2O Ru terpy bipy NH3 Ru terpy bipy NO 2 5 H 6 e Reactions EditAn important reaction is the acid base equilibrium yielding transition metal nitrite complexes LnMNO 2 2OH LnMNO2 H2OThis equilibrium serves to confirm that the linear nitrosyl ligand is formally NO with nitrogen in the oxidation state 3 NO 2 OH NO2 H2OSince nitrogen is more electronegative than carbon metal nitrosyl complexes tend to be more electrophilic than related metal carbonyl complexes Nucleophiles often add to the nitrogen 2 The nitrogen atom in bent metal nitrosyls is basic thus can be oxidized alkylated and protonated e g Ph3P 2 CO ClOsNO HCl Ph3P 2 CO ClOsN H OIn rare cases NO is cleaved by metal centers Cp2NbMe2 NO Cp2 Me Nb O NMe 2 Cp2 Me Nb O NMe 2 Cp2Nb O Me MeN NMe Nitrosylation of a heme thiolate steps in cell signaling by nitric oxide porphyrin is depicted as the square 16 Applications EditMetal nitrosyls are assumed to be intermediates in catalytic converters which reduce the emission of NOx from internal combustion engines This application has been described as one of the most successful stories in the development of catalysts 17 Structure of a dinitrosyl iron complex DNIC 18 Metal catalyzed reactions of NO are not often useful in organic chemistry In biology and medicine nitric oxide is however an important signalling molecule in nature and this fact is the basis of the most important applications of metal nitrosyls The nitroprusside anion Fe CN 5NO 2 a mixed nitrosyl cyano complex has pharmaceutical applications as a slow release agent for NO The signalling function of NO is effected via its complexation to haeme proteins where it binds in the bent geometry Nitric oxide also attacks iron sulfur proteins giving dinitrosyl iron complexes Thionitrosyls EditSeveral complexes are known with NS ligands Like nitrosyls thionitrosyls exist as both linear and bent geometries 19 References Edit Sodium Nitroprusside www drugs com The American Society of Health System Pharmacists Retrieved 21 October 2022 a b Hayton T W Legzdins P Sharp W B 2002 Coordination and Organometallic Chemistry of Metal NO Complexes Chem Rev 102 1 935 991 doi 10 1021 cr000074t PMID 11942784 a b Greenwood Norman N Earnshaw Alan 1997 Chemistry of the Elements 2nd ed Butterworth Heinemann pp 447 453 ISBN 978 0 08 037941 8 Ariyarathna Isuru R Miliordos Evangelos 15 July 2019 Electronic and geometric structure analysis of neutral and anionic metal nitric chalcogens The case of MNX series M Li Na Be and X O S Se Te Journal of Computational Chemistry 40 19 1740 1751 doi 10 1002 jcc 25829 PMID 30920017 S2CID 85546245 Ariyarathna Isuru 1 March 2021 First Principle Studies on Ground and Excited Electronic States Chemical Bonding in Main Group Molecules Molecular Systems with Diffuse Electrons and Water Activation using Transition Metal Monoxides a b Enemark J H Feltham R D 1974 Principles of structure bonding and reactivity for metal nitrosyl complexes Coord Chem Rev 1974 13 339 406 doi 10 1016 S0010 8545 00 80259 3 Mikhailov Artem A Wenger Emmanuel Kostin Gennadiy A Schaniel Dominik 2019 Room Temperature Photogeneration of Nitrosyl Linkage Isomers in Ruthenium Nitrosyl Complexes PDF Chemistry A European Journal 25 31 7569 7574 doi 10 1002 chem 201901205 PMID 30957917 S2CID 102349334 Herberhold Max 1972 Tetranitrosylchromium Cr NO 4 Angewandte Chemie International Edition in English 11 12 1092 1094 doi 10 1002 anie 197210921 Greenwood Norman N Earnshaw Alan 1997 Chemistry of the Elements 2nd ed Butterworth Heinemann p 449 ISBN 978 0 08 037941 8 Paul Gilmont Arthur A Blanchard 1946 Dicobalt Octacarbonyl Cobalt Nitrosyl Tricarbonyl and Cobalt Tetracarbomyl Hydride Inorganic Syntheses Inorg Synth Inorganic Syntheses Vol 2 p 238 doi 10 1002 9780470132333 ch76 ISBN 9780470132333 a href Template Cite book html title Template Cite book cite book a CS1 maint uses authors parameter link Richard R Thomas Ayusman Sen 1990 Acetonitrile Complexes of Selected Transition Metal Cations Inorganic Syntheses Inorg Synth Inorganic Syntheses Vol 28 pp 63 67 doi 10 1002 9780470132593 ch14 ISBN 9780470132593 a href Template Cite book html title Template Cite book cite book a CS1 maint uses authors parameter link Francine Agbossou Edward J O Connor Charles M Garner N Quiros Mendez Jesus M Fernandez Alan T Patton James A Ramsden J A Gladysz 1992 Cyclopentadienyl Rhenium Complexes Inorganic Syntheses Inorg Synth Inorganic Syntheses Vol 29 pp 211 225 doi 10 1002 9780470132609 ch51 ISBN 9780470132609 a href Template Cite book html title Template Cite book cite book a CS1 maint uses authors parameter link B F G Johnson K H Al Obadi 1970 Dihalogenodinitrosylmolybdenum and Dihalogenodinitrosyltungsten Inorganic Syntheses Inorg Synth Inorganic Syntheses Vol 12 pp 264 266 doi 10 1002 9780470132432 ch47 ISBN 9780470132432 a href Template Cite book html title Template Cite book cite book a CS1 maint uses authors parameter link James K Hoyano Peter Legzdins John T Malito 1978 h5 Cyclopentadienydnitrosyl Complexes of Chromium Molybdenum and Jungsten h5 Cyclopentadienydnitrosyl Complexes of Chromium Molybdenum and Tungsten Inorg Synth Inorganic Syntheses Vol 13 pp 126 131 doi 10 1002 9780470132494 ch21 ISBN 9780470132494 a href Template Cite book html title Template Cite book cite book a CS1 maint uses authors parameter link Dunn Peter L Cook Brian J Johnson Samantha I Appel Aaron M Bullock R Morris 2020 Oxidation of Ammonia with Molecular Complexes Journal of the American Chemical Society 142 42 17845 17858 doi 10 1021 jacs 0c08269 OSTI 1706682 PMID 32977718 S2CID 221938378 Walker F A 2005 Nitric Oxide Interaction with Insect Nitrophorins and Thoughts on the Electron Configuration of the FeNO6 Complex J Inorg Biochem 99 1 216 236 doi 10 1016 j jinorgbio 2004 10 009 PMID 15598503 Kaspar Jan Fornasiero Paolo Hickey Neal 2003 Automotive Catalytic Converters Current Status and Some Perspectives Catalysis Today 77 4 419 449 doi 10 1016 S0920 5861 02 00384 X a href Template Cite journal html title Template Cite journal cite journal a CS1 maint uses authors parameter link Jessica Fitzpatrick Eunsuk Kim 2015 Synthetic Modeling Chemistry of Iron Sulfur Clusters in Nitric Oxide Signaling Acc Chem Res 48 8 2453 2461 doi 10 1021 acs accounts 5b00246 PMID 26197209 a href Template Cite journal html title Template Cite journal cite journal a CS1 maint uses authors parameter link Ng Ho Yuen Cheung Wai Man Kwan Huang Enrique Wong Kang Long Sung Herman H Y Williams Ian D Leung Wa Hung 2015 Ruthenium chalcogenonitrosyl and bridged nitrido complexes containing chelating sulfur and oxygen ligands Dalton Transactions 44 42 18459 18468 doi 10 1039 C5DT02513C PMID 26442594 Retrieved from https en wikipedia org w index php title Metal nitrosyl complex amp oldid 1122885204, wikipedia, wiki, book, books, library,

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