Treatment of CptRh(PMe3)Cl2(1) (Cpt=5η-tBu2C5H3) with [Et4N]2Se6 in DMF solution leads to the for-mation of cyclo-tetraselenido half-sandwich rhodium com-plexes CptRh(PMe3)(Se4) (2). The elimination of 2 with ex-cess of nBu3P results in cyclo-diselenido rhodium complex CptRh(PMe3)(Se2) (3). 1 reacts with [nBu4N]2Te5 in DMF solution to yield cyclo-ditellurido rhodium complex CptRh (PMe3)(Te2) (4) in which carbon atom from CH2C12 can be inserted into Te-Te bond to form CptRh(PMe3)(TeCH2Te) (5). The new complexes 2-5 have been characterized by their IR, EI-MS, and 1H, 13C, 31P, 103Rh NMR spectra as well as ele-mental analysis.
Halfsandwich iron dicarbonyl complex [η 5-C_5H_3(t-Bu)_2]Fe(CO)_2Cl(1) reacts with 1, 2-dilithium diseleno carborane Li_2Se_2C_2B_ 10H_ 10(2) to give a binuclear iron carborane complex [η 5-C_5H_3(t-Bu)_2]_2Fe_2(CO)_3·Se_2C_2B_ 10H_ 10(3). The X-ray diffraction analysis of complex 3 reveals that one of the iron atoms is chiral.
The reactions of [CptRhCl(m-Cl)]2 (1) (Cpt = tBu2C5H3) with Li2E2C2B10H10 (E = S, Se) lead to the green 16-electron dichalcogenolate complexes CptRh(E2C2B10H10) [E = S(2a), Se(2b)]. The 16-electron complexes 2a and 2b can take up two-electron donor ligands such as tert-butyl isoni-trile and carbon monoxide to give the 18-electron dichalco-genolate derivatives Cpt(L)(E2C2B10H10) [L = tBuNC, E = S(3a), Se(3b); L = CO, E = S(4a), Se(4b)]. The molecular structures of complexes 2a and 3a were determined by X-ray crystal structure analysis. The molecular structure of 16- electron complex 2a shows the pseudoaromatic system in IrSe2C2 five numbered ring.
KONG Qingan, JIN Guoxin, CAI Shuyi & WENG Linhong Laboratory of Molecular Catalysis and Innovative Material, Chemistry Department, Fudan University, Shanghai 200433, China Correspondence should be addressed to Jin Guoxin (e-mail: gxjin@ fudan.edu.cn)
The reaction of \[Cp\+\%t\%RhCl\-2\]\-2(1) (Cp\+\%t\%=η\+5\|\{\}\+\%t\%Bu\-2C\-5\|H\-3) with 1,2\|dilithium dichalcogenolate carborane Li\-2E\-2C\-2B\-\{10\}H\-\{10\}(E=S, Se) afforded the 16\|electron rhodium(Ⅲ) half\|sandwich complexes \{Cp\+\%t\%Rh(E\-2C\-2B\-\{10\}H\-\{10\})\}\3a), Se(3b)\]. 18\|Electron trimethyl phosphine rhodium(Ⅲ) half\|sandwich complexes Cp\+\%t\%Rh(PMe\-3)(E\-2C\-2B\-\{10\}H\-\{10\})\. 18\|Electron trimethyl phosphine rhodium(Ⅲ) half\|sandwich complexes Cp\+\%t\%Rh(PMe\-3)(E\-2C\-2B\-\{10\}H\-\{10\})\4a), Se(4b), Te(4c)\] can be synthesized both by addition of PMe\-3 into 16\|electron complexes can be synthesized both by addition of PMe\-3 into 16\|electron complexes 3a, 3b and by the reaction Cp\+\%t\%Rh(PMe\-3)Cl\-2(2) with Li\-2E\-2C\-2B\-\{10\}H\-\{10\}(\{E=S\}, Se, Te). The molecular geometry of 4b was determined by X\|ray diffraction structural analysis.
