| Abstract: | Synthesis of Trimethylsilyl Substituted Polyhedra of Calcium, Tin(II), and Phosphorus The reaction of calcium-bis[bis(trimethylsilyl)amide] with bis(trimethylsilyl)phosphane in thf yields the heteroleptic, dimeric (tetrahydrofuran-O)calcium-bis(trimethylsilyl)amidebis(trimethylsilyl)phosphanide 1 (triclinic, P 1 , a = 1066,6(2), b = 1141,3(2), c = 1226,6(2)pm, α = 97,78(3)°, β = 107,47(3)°, γ = 101,12(3)°, Z = 1 dimer). The bridging phosphanide-substituent displays with Ca? P bond lengths of 292,6 and 300,5 pm a distortion of the four-membered Ca2P2-cycle. The reaction with another equivalent of HP(SiMe3)2 in thf leads to the formation of tetrakis(tetrahydrofuran-O)calcium-bis[bis(trimethylsilyl)phosphanide] 2 mit Ca? P distances of 292 pm (monoclinic, P21/c, a = 1626,0(3), b = 1295,3(4), c = 2039,5(5) pm, β = 102,60(2)°, Z = 4). The performance of the reaction in the presence of bis[bis(trimethylsilyl)amino]stannylene yields heterobimetallic compounds with a central polyhedron of Ca-, Sn- and P-atoms. Dependent on the Sn/Ca ratio the isolation of tris(trimethylsilyl)phosphane as well as bis[tris(tetrahydrofuran-O)calcium]-ditin(II)-tetrakis(μ3-trimethylsilylphosphandiide) 3 with a central dicalcia-distanna-tetraphosphacubane-fragment or (thf)2CaSn2[μ-P(SiMe3)2]2[μ3-PSiMe3]2 4 (orthorhombic, Pnma, a = 2247,7(2), b = 1868,9(1), c = 1168,0(1) pm, Z = 4), respectively, succeeds. The Ca? P distances lie at 291 pm. |
