Ligand-to-Metal Ratio Controlled Assembly of Cobalt Complexes Containing ortho-Carborane Thiolato and Butyl Thiolato Ligands

Abstract

Treatment of ortho-carborane, n-butyl lithium, sulfur, and CpCo(CO)I(2) with differing ratios led to four new compounds [(CpCoS(2)C(2)B(10)H(10))(CpCoSC(2)B(10)H(11))(SC(4)H(9))] (3), [(CpCo)(2)S(2)(S(2)C(2)B(10)H(10)) (SC(2)B(10)H(10))(SC(4)H(9))] (4), [(CpCo)(2)Co(SC(4)H(9))(6)](+)[Co(S(2)C(2)B(10)H(10))(2)](-) (5), and [(CpCo)(2)Co(SC(2)B(10)H(11))(SC(4)H(9))(5)](+)[Co(S(2)C(2)B(10)H(10))(2)](-) (6). Compound 3 contains a rhombic Co(2)(mu(2)-S)(2) core and can be considered as an adduct of the two 16e half-sandwich monomers CpCo(S(2)C(2)B(10)H(10)) (1) and CpCo(SC(4)H(9))(SC(2)B(10)H(11)). Compound 4 is a trinuclear complex containing a cuboidal [Co(3)(mu(3)-S)(2)(mu-S)(2)] core, and one cobalt atom is coordinated by six sulfur atoms in a distorted octahedral geometry. Compound 5 consists of a linear-type trinuclear cobalt(III) monocation bridged by six n-butyl thiolato units and a square-planar cobalt(III) monoanion [Co(S(2)C(2)B(10)H(10))(2)](-). However, in 6, one ortho-carborane monothiolato ligand [SC(2)B(10)H(11)](-) has replaced one n-butyl thiolato ligand in 5. This leads to a nonlinear arrangement of the three cobalt atoms in the cation and the nonplanar [Co(S(2)C(2)B(10)H(10))(2)](-) anion in 6. Interestingly, the treatment of the 16e half-sandwich CpCo(S(2)C(2)B(10)H(10)) (1) by [N(n-Bu)(4)]Br afforded the ionic compound 7, [N(n-Bu)(4)](+)[Co(S(2)C(2)B(10)H(10))(2)](-), containing a square-planar anion.

Diverse reactivities of aromaticity–unsaturation coexisted metalladithiolene rings

“…Adduct formations of [LM(S 2 C 2 B 10 H 10 )] complexes by diazoalkane or quadricyclane were reported by Kang and by Yan et al [100,101] (Scheme 9). Furthermore, diverse reactivities of [LM(S 2 C 2 B 10 H 10 )] complexes with acetylene derivatives were intensively developed by Herberhold,Wrackmeyer [102], and Bregadze et al [103] (Scheme 9). In the typical dithiolene complexes such as [LM(S 2 C 2 R 2 )], only the electron-poor acetylene (e.g.…”

Reactivity of a 16‐Electron CpCo Half‐Sandwich Complex Containing a Chelating 1,2‐Dicarba‐closo‐dodecaborane‐1,2‐diselenolate Ligand towards FcC(O)C≡CH

“…An analogous structure of a sulfur complex [CpCo(S 2 C 2 B 10 H 10 )][{CpCo(SC 2 B 10 H 11 )}(n-BuS)] has been previously reported by our group. [10] …”

“…Another remarkable feature of 5 is that one apex at the B(6) site of the carborane has been lost to generate a nido-C 2 B 9 cage. Conversion of a neutral closo-C 2 B 10 H 10 cage to a negatively charged nido-C 2 B 9 H 10 -cluster has been extensively reported if an alcohol or a nucleophilic reagent is present. [1a,6b,12] As confirmed in the solid-state structure, the unusual face-bridging hydrogen binding to the three B atoms at the open face is observed at -2.87 ppm in the 1 H NMR spectrum.…”

Boron, aluminium, gallium, indium and thallium

“…In the presence of air, water and silica this intermediate converts to two new 16e complexes, bearing new types of functionalised groups (VII-VIII). 96,97 Treatment of ortho-carborane, n-butyl lithium, sulfur, and CpCo(CO)I 2 , in differing ratios has led to the formation and isolation of four new compounds…”

“…À , all of which have been structurally characterised. 98 The synthesis of new pyridine-substituted carboranylmethylamines and their use in the formation of palladium complexes for the Suzuki coupling reaction has been described. 99 Boryl, borylene and related systems A review describing recent advances in the synthesis of organoborane polymers for optical, electronic, and sensory applications has been published in 2010.…”