Dinuclear copper complexes: coordination of Group 14 heteroborates

Abstract

Dicopper(i) complexes with the chelating dmapm ligand [dmapm = 1,1-bis{di(o-N,N-dimetylanilinyl)phosphino}methane] have been synthesized and characterized structurally. Synthesis of the acetonitrile adduct [Cu2(μ-dmapm)(CH3CN)2][BF4]2 () has been presented and the dicopper electrophile has been used as the starting material in reaction with Group 14 heteroborates. Coordination of the closo-borates at the dicopper moiety resulted in different molecular structures with varying CuCu distances. In the case of the side on coordinated stanna-closo-dodecaborate the tin vertex has been characterized by (119)Sn Mössbauer spectroscopy and the nucleophilicity at the tin was established in reaction with a molybdenum carbonyl complex.

Stepwise Introduction of Cyano Groups into nido‐ and closo‐Undecaborate Clusters

“…[9] The latter have been intensively used as ligands in coordination chemistry. [10] The [closo-1-CB 11 H 12 ] À anion and its derivatives are widely applied, [11] for example, in coordination chemistry.T hey act as weakly coordinating anions [8,12] or as ligands, for example, in [Ag 7 (12-CC-closo-1-CB 11 H 11 ) 4 (3,5-Me 2 Py) 10 ] À . [13] Aufbau reactions with transition metal (M) fragments to give {closo-MB 11 } clusters have been described as well.…”

“…Important Aufbau reactions are the insertion of dichlorocarbene into the open face of the { nido ‐B 11 } cage to give the carba‐ closo ‐dodecaborate anion [ closo ‐1‐CB 11 H 12 ] − [6–8] and related reactions that provide access to the anions [ closo ‐1‐XB 11 H 11 ] 2− (X=Ge, Sn, Pb) . The latter have been intensively used as ligands in coordination chemistry . The [ closo ‐1‐CB 11 H 12 ] − anion and its derivatives are widely applied, for example, in coordination chemistry.…”

Oxidation of germa- and stanna-closo-dodecaborate

“…Heteroborane cluster chemistry is an active field of research and many interesting studies have been published in recent years. [1][2][3][4][5][6][7][8][9][10] In heteroborane clusters a BH vertex of a borane cluster skeleton is replaced by a main group element or a transition metal. Following the isolobal principle a BH unit can for example be substituted by a Ge atom or an anionic BH − unit by an N atom.…”