Thermal and Photolytic Reactions of Nitrosyl-Carbonyl Complexes of Rhodium and Iridium with Triphenylphosphine

Mitsuru Kubota; Michael K. Chan; David C. Boyd; Kent R. Mann

doi:10.1021/ic00267a009

Thermal and Photolytic Reactions of Nitrosyl-Carbonyl Complexes of Rhodium and Iridium with Triphenylphosphine

Mitsuru Kubota
, Michael K. Chan
, David C. Boyd
, Kent R. Mann

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

Abstract

The photolysis of [Rh(NO)(CO)(PPh₃)₂] in the presence of PPh₃in dichloromethane results in the expulsion of NO rather than CO and the formation of trans-[Rh(CO)Cl(PPh₃)₂]. The thermal reaction and photoreaction of [Ir(NO)(CO)Cl(PPh₃)₂]BF₄(1) with PPh₃lead to dissociation of NO and the formation of the Ir(II) radical [Ir(CO)Cl(PPh₃)₃]BF₄(2). The demonstration of the homolytic cleavage of the Ir-NO bond of 1 provides support for the proposal that the photodissociation of NO instead of CO in the compounds [M(NO)(CO)(PPh₃)₂] (where M is Rh or Ir) proceeds from a charge-transfer state that has a bent M-N-0 bond.

Original language	English (US)
Pages (from-to)	3261-3264
Number of pages	4
Journal	Inorganic chemistry
Volume	26
Issue number	20
DOIs	https://doi.org/10.1021/ic00267a009
State	Published - Oct 1 1987

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title = "Thermal and Photolytic Reactions of Nitrosyl-Carbonyl Complexes of Rhodium and Iridium with Triphenylphosphine",

abstract = "The photolysis of [Rh(NO)(CO)(PPh3)2] in the presence of PPh3in dichloromethane results in the expulsion of NO rather than CO and the formation of trans-[Rh(CO)Cl(PPh3)2]. The thermal reaction and photoreaction of [Ir(NO)(CO)Cl(PPh3)2]BF4(1) with PPh3lead to dissociation of NO and the formation of the Ir(II) radical [Ir(CO)Cl(PPh3)3]BF4(2). The demonstration of the homolytic cleavage of the Ir-NO bond of 1 provides support for the proposal that the photodissociation of NO instead of CO in the compounds [M(NO)(CO)(PPh3)2] (where M is Rh or Ir) proceeds from a charge-transfer state that has a bent M-N-0 bond.",

author = "Mitsuru Kubota and Chan, \{Michael K.\} and Boyd, \{David C.\} and Mann, \{Kent R.\}",

year = "1987",

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T1 - Thermal and Photolytic Reactions of Nitrosyl-Carbonyl Complexes of Rhodium and Iridium with Triphenylphosphine

AU - Kubota, Mitsuru

AU - Chan, Michael K.

AU - Boyd, David C.

AU - Mann, Kent R.

PY - 1987/10/1

Y1 - 1987/10/1

N2 - The photolysis of [Rh(NO)(CO)(PPh3)2] in the presence of PPh3in dichloromethane results in the expulsion of NO rather than CO and the formation of trans-[Rh(CO)Cl(PPh3)2]. The thermal reaction and photoreaction of [Ir(NO)(CO)Cl(PPh3)2]BF4(1) with PPh3lead to dissociation of NO and the formation of the Ir(II) radical [Ir(CO)Cl(PPh3)3]BF4(2). The demonstration of the homolytic cleavage of the Ir-NO bond of 1 provides support for the proposal that the photodissociation of NO instead of CO in the compounds [M(NO)(CO)(PPh3)2] (where M is Rh or Ir) proceeds from a charge-transfer state that has a bent M-N-0 bond.

AB - The photolysis of [Rh(NO)(CO)(PPh3)2] in the presence of PPh3in dichloromethane results in the expulsion of NO rather than CO and the formation of trans-[Rh(CO)Cl(PPh3)2]. The thermal reaction and photoreaction of [Ir(NO)(CO)Cl(PPh3)2]BF4(1) with PPh3lead to dissociation of NO and the formation of the Ir(II) radical [Ir(CO)Cl(PPh3)3]BF4(2). The demonstration of the homolytic cleavage of the Ir-NO bond of 1 provides support for the proposal that the photodissociation of NO instead of CO in the compounds [M(NO)(CO)(PPh3)2] (where M is Rh or Ir) proceeds from a charge-transfer state that has a bent M-N-0 bond.

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DO - 10.1021/ic00267a009

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SN - 0020-1669

VL - 26

SP - 3261

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JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 20

ER -

Thermal and Photolytic Reactions of Nitrosyl-Carbonyl Complexes of Rhodium and Iridium with Triphenylphosphine

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