Synthesis and reactivity of organotin compounds containing the C,P-chelating o-carboranylphosphino ligand [o-C2B10H10PPh2-C,P] (CabC,P). X-ray structures of (CabC,CH2P)SnMe2Br, [(CabC,P)SnMe2]2Pd, and [(CabC,P)SnMe2]Pd(PEt3)Cl

Article abstract of DOI:10.1021/om0007872

The triorganotin halides (Cab^C,P)SnMe₂X (2a, X = Cl; 2b, X = Br) and a tetraorganotin compound (Cab^C,P)SnMe₃ (7), containing the o-carboranylphosphino ligand (Cab^C,P), have been prepared by the reaction of LiCab^C,P (1) with Me₂SnX₂ and Me₃SnCl, respectively. ¹H, ¹³C, ³¹P, and ¹¹⁹Sn NMR spectroscopy indicate that the tin centers in 2a and 2b are pentacoordinate as a result of intramolecular Sn-P coordination, whereas the tin center in 7 is tetracoordinate. The substitution reactions of 2a using NaI, NaN₃, NaCpFe(CO)₂, and NaB(CN)H₃ afforded the substituted products (Cab^C,P)SnMe₂X (3, X = I; 4, X = N₃; 5, X = CpFe(CO)₂; 6, X = H). The Wurtz-type coupling reaction of 2a with sodium afforded the distannane. The reaction of the distannane 10 with Pd₂(dba)₃·CHCl₃ afforded the bis(stannyl)-palladium complex 11. When compounds 2a and 2b were employed in the reaction with Pd₂(dba)₃, the halo-bridged metal complexes 12a and 12b were isolated. The crystal structures of 9b, 11, and 13 were determined by X-ray structural studies. As a result of the Sn-P interaction, the tin atom in 9b exhibits a distorted trigonal-bipyramidal configuration.