中性和两性离子半夹心 Ir、Rh 配合物，由 P、S 取代的邻-carboranyl 配体支撑：合成、表征和反应性。

Neutral and zwitterionic half-sandwich Ir, Rh complexes supported by P,S-substituted o-carboranyl ligands: Synthesis, characterization and reactivity.

机构信息

Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Advanced Materials Laboratory, Fudan University, 200433, Shanghai, PR China.

出版信息

Dalton Trans. 2010 Feb 28;39(8):1954-61. doi: 10.1039/b918272a. Epub 2010 Jan 5.

DOI:10.1039/b918272a

PMID:20148211

Abstract

The neutral CpM(Cl)(1-PPh(2)-2-S-1,2-C(2)B(10)H(10)) and zwitterionic CpM(3-OCH(3)-7-PPh(2)-8-S-7,8-C(2)B(9)H(9)) (Cp* = eta(5)-C(5)Me(5), M = Ir, Rh, 1-PPh(2)-2-S-1,2-C(2)B(10)H(10) = [1-(diphenylphosphino)-2-thiolato)-1,2-dicarba-closo-carborane], 3-OCH(3)-7-PPh(2)-8-S-7,8-C(2)B(9)H(9) = 3-(methoxyl)-7-(diphenylphosphino)-8-(thiolato)-7,8-dicarba-nido-carborane) were synthesized and fully characterized. The 18-electron neutral closo-carborane complexes CpM(Cl)(1-PPh(2)-2-S-1,2-C(2)B(10)H(10)) (M = Ir (), Rh ()) can be easily deboronated to result in the formation of reactive 16-electron zwitterionic nido-carborane complexes [CpM(3-OCH(3)-7-PPh(2)-8-S-7,8-C(2)B(9)H(9))] (M = Ir (), Rh()). The oxidation of with O(2) gas afforded the corresponding sulfone complex in high yields. Utilization of its unsaturated feature in 16-electron zwitterionic nido-carborane complexes offers a potential strategy to synthesize new types of organometallic complexes.

摘要

中性 CpM(Cl)(1-PPh(2)-2-S-1,2-C(2)B(10)H(10)) 和两性离子 CpM(3-OCH(3)-7-PPh(2)-8-S-7,8-C(2)B(9)H(9)) (Cp*=eta(5)-C(5)Me(5), M=Ir, Rh, 1-PPh(2)-2-S-1,2-C(2)B(10)H(10)=[1-(二苯基膦基)-2-硫代]-1,2-二碳杂-closo-卡硼烷], 3-OCH(3)-7-PPh(2)-8-S-7,8-C(2)B(9)H(9)=3-(甲氧基)-7-(二苯基膦基)-8-(硫代)-7,8-二碳杂-nido-卡硼烷）被合成并进行了充分的表征。18 电子中性 closo-卡硼烷配合物 CpM(Cl)(1-PPh(2)-2-S-1,2-C(2)B(10)H(10))（M=Ir()，Rh()）很容易脱硼，形成反应性的 16 电子两性离子 nido-卡硼烷配合物 [CpM(3-OCH(3)-7-PPh(2)-8-S-7,8-C(2)B(9)H(9))]（M=Ir()，Rh()）。用 O(2)气体氧化得到相应的砜配合物，产率很高。利用其在 16 电子两性离子 nido-卡硼烷配合物中的不饱和特性，为合成新型金属有机配合物提供了一种潜在的策略。