trans-carbonyl(sulfonylnitride)bis(triphenylphosphine)rhodium(I) | 136214-86-3

• 英文名称: trans-carbonyl(sulfonylnitride)bis(triphenylphosphine)rhodium(I)
• CAS: 136214-86-3
• 化学式: C₃₇H₃₀NO₃P₂RhS
• 分子量: 733.569
• InChiKey: JJCMKJNECNQATP-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  trans-carbonyl(sulfonylnitride)bis(triphenylphosphine)rhodium(I) 在 PPh₃ 作用下， 以 乙腈 为溶剂， 以67%的产率得到trans-carbonyl(thionitro)bis(triphenylphosphine)rhodium(I)
  参考文献：
  名称：

  Coordination chemistry of NSO−, NSO2− and S3N− ligands: comparison of electronic structure of RhNSO, RhSH and RhCl complexes

  摘要：

  CsNSO2 reacts with fluoro complexes, trans-[M(CO)F(PPh3)2] (M = Rh, Ir) to give sulfonylnitrido complexes, trans-[M(CO)(NSO2)(PPh3)2] which react with triphenylphosphine to afford thionitro complexes, trans-[M(CO)(NSO)(PPh3)2]. The thionitro complexes are also prepared by the reaction of CsNSO2 with hydrido complexes, [MH(CO)(PPh3)3]. Reaction of CsNSO2 with [RuH2(CO)(PPh3)2] yields [Ru(CO)(NSO2)2(PPh3)2]. The sulfonylnitrido complexes of the type Cs2[M'(NS)(NSO2)2Cl3] (M' = Ru, Os) are prepared by the reaction of CsNSO2 and [M'(NS)Cl3]. The reactions of heptasulfurimide with [RhCl(PPh3)3] and [Rh(CO)Cl(PPh3)2] afford disulfidothinitrato complexes [Rh(S3N)(PPh3)2] and [Rh(CO)(S3N)(PPh3)2], respectively. CNDO/2 molecular orbital calculations have been performed on the model systems trans-[Rh(CO)L(PH3)2] (L = NSO, SH, Cl) in order to investigate the nature and energetics of the interaction between rhodium and NSO, SH, Cl ligands. The computed trends for Rh-X, Rh-C and C-O bond strengths, as measured by Wiberg indices and charge distributions, suggest that the strength of the coordination bond Rh-L increases in the order [Rh-NSO] < [Rh-Cl] < [Rh-SH] and the strength of the Rh-C bond increases in the order [Rh(CO)Cl(PH3)2] < [Rh(CO)(NSO)-(PH3)2] < [Rh(CO)(SH)(PH3)2]. The trend in C-O bond strength is [Rh(CO)Cl(PH3)2] > [Rh(CO)(NSO)-(PH3)2] > [Rh(CO)(SH)(PH3)2]. The NSO group is the worst pi-acceptor amongst the three ligands.

  DOI：

  10.1016/s0020-1693(00)90151-8
• 作为产物：
  描述：

  fluorocarbonylbis(triphenylphosphine)rhodium(I) 、 cesium sulfonylnitride 以 乙腈 为溶剂， 以85%的产率得到trans-carbonyl(sulfonylnitride)bis(triphenylphosphine)rhodium(I)
  参考文献：
  名称：

  Coordination chemistry of NSO−, NSO2− and S3N− ligands: comparison of electronic structure of RhNSO, RhSH and RhCl complexes

  摘要：

  CsNSO2 reacts with fluoro complexes, trans-[M(CO)F(PPh3)2] (M = Rh, Ir) to give sulfonylnitrido complexes, trans-[M(CO)(NSO2)(PPh3)2] which react with triphenylphosphine to afford thionitro complexes, trans-[M(CO)(NSO)(PPh3)2]. The thionitro complexes are also prepared by the reaction of CsNSO2 with hydrido complexes, [MH(CO)(PPh3)3]. Reaction of CsNSO2 with [RuH2(CO)(PPh3)2] yields [Ru(CO)(NSO2)2(PPh3)2]. The sulfonylnitrido complexes of the type Cs2[M'(NS)(NSO2)2Cl3] (M' = Ru, Os) are prepared by the reaction of CsNSO2 and [M'(NS)Cl3]. The reactions of heptasulfurimide with [RhCl(PPh3)3] and [Rh(CO)Cl(PPh3)2] afford disulfidothinitrato complexes [Rh(S3N)(PPh3)2] and [Rh(CO)(S3N)(PPh3)2], respectively. CNDO/2 molecular orbital calculations have been performed on the model systems trans-[Rh(CO)L(PH3)2] (L = NSO, SH, Cl) in order to investigate the nature and energetics of the interaction between rhodium and NSO, SH, Cl ligands. The computed trends for Rh-X, Rh-C and C-O bond strengths, as measured by Wiberg indices and charge distributions, suggest that the strength of the coordination bond Rh-L increases in the order [Rh-NSO] < [Rh-Cl] < [Rh-SH] and the strength of the Rh-C bond increases in the order [Rh(CO)Cl(PH3)2] < [Rh(CO)(NSO)-(PH3)2] < [Rh(CO)(SH)(PH3)2]. The trend in C-O bond strength is [Rh(CO)Cl(PH3)2] > [Rh(CO)(NSO)-(PH3)2] > [Rh(CO)(SH)(PH3)2]. The NSO group is the worst pi-acceptor amongst the three ligands.

  DOI：

  10.1016/s0020-1693(00)90151-8