Ligand-to-metal ratio controlled assembly of cobalt complexes containing ortho-carborane thiolato and butyl thiolato ligands.
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.
Li
Yuguang
Y
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Jiangsu 210093, China.
Jiang
Qibai
Q
Li
Yizhi
Y
Shen
Xujie
X
Yan
Hong
H
Bregadze
Vladimir I
VI
D003035:Cobalt / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D008024:Ligands; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D003035:Cobalt