Rhodium-Induced Selective B(3)/B(6)-Disubstitution ofortho-Carborane-1,2-dithiolate

Abstract

The various reactive sites in the 16 e complex 1 invite addition reactions with alkynes. After addition of 2 to one of the Rh-S bonds, B-H activation takes place which finally leads to the complex 3, in which a B(3)/B(6)-disubstituted o-carborane cage is present for the first time.

Synthesis and characterization of half-sandwich Rh, Ir complexes containing mono-thiolate-ortho-carborane ligand

“…2.4200(15) Å are a litter longer than that of Rh(1)eCl(1) 2.388(2) Å, Rh(2)eCl(2) 2.375(2) Å, which are in agreement with previous values for them in analogous complexes [45,46], The separation of the Ir(1)eCl(1), Ir(1)eS(1), Ir(2)eCl(2, Ir(2)eS(1) are in agreement with these of analogous complexes [47,48]. Tatsumi and co-workers [9,10].…”

Tetrametallic clusters (Ir2Rh2) through an ancillary ortho-carborane-1,2-dichalcogenolato ligands

“…4 A number of mononuclear 16-electron Cp and Cp* half-sandwich complexes of Co, Rh and Ir have been described which contain a bidentate, chelating 1,2-dicarba-closododecaborane-1,2-dichalcogenolato ligand, [(B 10 H 10 )C 2 E 2 ] 2− (E = S, Se) and a "pseudo-aromatic" metalladichalcogenolene fivemembered ring. 4 These compounds have been used as models to study the insertion of alkynes into one of the metal-sulfur bonds; this may lead to the formation of a metal-to-boron bond or substitution of the carborane cage in the positions of B(3)/B (6). 5,6 In recently, we have developed a methodology to build up polynuclear frameworks, containing metal-metal Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Fudan University, 200433, Shanghai, P. R. China.…”

“…4 These compounds have been used as models to study the insertion of alkynes into one of the metal-sulfur bonds; this may lead to the formation of a metal-to-boron bond or substitution of the carborane cage in the positions of B(3)/B (6). 5,6 In recently, we have developed a methodology to build up polynuclear frameworks, containing metal-metal Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Fudan University, 200433, Shanghai, P. R. China. E-mail: gxjin@fudan.edu.cn;Fax: +86-21-65641740;Tel: +86-21-65643776 5 The incorporation of the 1,2-dithiolato or 1,2-diselenolato structural unit into the bulky closo-dicarbadodecaborane ligand protects the inner coordination sphere and stabilized the metalmetal bond, which has occasionally been observed at dithiolene ligands.…”

Rational synthesis of trinuclear (WIr2) cluster from the 16-electron half-sandwich complex Cp*Ir[Se2C2(B10H10)]

“…A number of mononuclear 16 electron Cp and Cp* half-sandwich complexes of Co [3], Rh [4] and Ir [5] have been described which contain a bidentate 1,2-dichalcogenolate carborane ligands, [(B 10 H 10 )C 2 E 2 ] 2À and a ''pseudo-aromatic'' metalladichalcogenolene five-membered ring. These complexes have been used as models to study the insertion of alkynes into one of the metal-sulfur bonds [6]; this may lead to the formation of a metal-to-boron bond and /or substitution of the carborane cage in the positions of B(3)/B(6) [7]. On the other hand, no reports on heteronuclear metal-metal bond formation by the ''pseudo-aromatic'' metallacycle complexes are available to our knowledge.…”