Rhodium(i) complexes with carborane-substituted P,N ligands: investigations of electronic structure and dynamic behaviour

Abstract

Two distorted square-planar RhI complexes (1 and 2) were obtained from [{RhCl(η4-cod)}2] and the respective P,N ligands.

Accessing the First nido‐Carborane‐Substituted Diphosphetane: A Ligand and Synthon for nido‐Carboranylphosphanes

“…These bis‐phosphanes are the first examples of nido ‐carboranyl bis‐phosphanes incorporating P−S and P−Se single bonds. Since the closo analogues of 5 b and 5 c showed a rich coordination chemistry towards Cu I , Ag I and Rh I , we expect 5 b and 5 c to be versatile multidentate ligands as well. Exemplarily, 5 b was shown to act as tetradentate P , N ligand in the copper(I) complex 9 .…”

Rh(I) Complexes in Catalysis: A Five-Year Trend

“…Suitable further substitution with a "hard" donor such as nitrogen could afford hemilabile ligands, which are particularly useful in catalysis. The ortho-carborane backbone was thus exploited to build a series of P,N ligands, possibly also bearing a chiral centre [85]. The respective Rh(I) complexes (Scheme 9) were thoroughly studied to elucidate their properties and tested in the dehydrocoupling reactions of amineboranes, and although they seem to be less active and selective than the reference complex [Rh(COD)Cl] 2 , their highly distorted square planar structure and the presence of hemilabile ligands could make them useful for other catalytic applications.…”

Carboranylphosphines: B9‐Substituted Derivatives with Enhanced Reactivity for the Anchoring to Dendrimers

“…[19] Especially, the easily accessible 1,2-bisphosphanyl-substituted carboranes (ortho isomers) are a family of versatile compounds with appealing features based on the carborane scaffold such as their adaptable CÀ C bond length, their electron-withdrawing effect, and the ability of hydridic BÀ H groups to engage in metal bonding. [20] The carborane scaffold further enhances the stability of phosphines towards oxygen in contrast to alkyl-and aryl-substituted phosphines. Certain compounds such as 1,2bis(chlorophosphino)-ortho-carborane, first reported in 1963, [13] are even inert against the reaction with sulfur up to 200 °C.…”

“…Substitution of the carbon‐bound hydrogen atoms in carboranes by different heteroatoms such as carbon, nitrogen, oxygen, phosphorus, and sulfur already yielded a wide scope of PP, [13–15] PN, [16] PS, [17] PC, [18] and other ligands for transition metal complexes and catalytically active metals [19] . Especially, the easily accessible 1,2‐bisphosphanyl‐substituted carboranes ( ortho isomers) are a family of versatile compounds with appealing features based on the carborane scaffold such as their adaptable C−C bond length, their electron‐withdrawing effect, and the ability of hydridic B−H groups to engage in metal bonding [20] . The carborane scaffold further enhances the stability of phosphines towards oxygen in contrast to alkyl‐ and aryl‐substituted phosphines.…”