150264-61-2Relevant academic research and scientific papers
Synthesis and structures of main group cage compounds containing boron, silicon, and phosphorus atoms
Dou, Danan,Kaufmann, Bernhard,Duesler, Eileen N.,Chen, Tuqiang,Paine, Robert T.,N?th
, p. 3056 - 3067 (2008/10/08)
The reactions of lithium salts [(i-Pr2N)BP(H)B(N-i-Pr2)PLi·DME] and [tmpBP(H)B(tmp)PLi·DME] (tmp = 2,2,6,6-tetramethylpiperidino) with organylhalosilanes have been surveyed, and silyl-substituted diphosphadiboretanes of the general types R2NBP(H)B(NR2)PSiR′3 (R2N = i-Pr2N, tmp; SiR′3 = SiMe2Ph) and R2NBP(H)B(NR2)PSiR′2-Cl (R2N = i-Pr2N, tmp; SiR′2Cl = SiMe2Cl, SiPh2Cl, Me2SiSiMe2(Cl)) have been isolated and characterized. Dehydrohalogenation of the latter class of compounds with t-BuLi provides an efficient route to new bicyclic cage compounds P2(BNR2)2(SiR2) and P2(BNR2)2[Si(R)2SiR2]. Alternatively, the cage compounds P2(tmpB)2SiR2 (R2 = Ph2, Me2, Ph(Me)) have been obtained by combination of the dipotassium salt K2[tmpBPB(tmp)P] and R2SiCl2. The coordination chemistry of the ligands has been surveyed, and a series of Fe(CO)4·L complexes has been isolated. Attempts to form bimetallic complexes were unsuccessful. The structures of several compounds have been determined by single-crystal X-ray diffraction techniques with Mo Kα radiation (λ = 0.710 73 A?): P2(i-Pr2NB)2(SiPh2), C24H38B2N2P2Si, crystallized in the triclinic space group P1 with a = 11.116(2) A?, b = 11.436(2) A?, c = 14.225(2) A?, α= 67.28(1)°, β = 67.66(1)°, γ = 61.10(1)°, and z = 2; P2(tmpB)2SiPh2, C30H46B2N2P2Si, crystallized in the orthorhombic space group Pbca with a = 14.445(9) A?, b = 19.18(2) A?, c = 23.25(2) A?, and Z = 8; P2(tmpB)2(SiMe2)2, C22H48B2N2P2Si 2, crystallized in the orthorhombic space group Pnma with a = 11.375(2) A?, b = 14.977-(2) A?, c = 16.939(4) A?, and Z = 4; i-Pr2NBP(H)B(N-i-Pr2)PSi(Me)2Si(Me) 2PB(N-i-Pr2)P(H)BN-i-Pr2, C14H35B2N2P2Si, crystallized in the monoclinic space group P21/n with a = 10.994(2) A?, b = 15.320(2) A?, c = 13.389(3) A?, β = 101.93(1)°, and Z = 4; P2(i-Pr2NB)2(SiMe2)2, C16H40B2N2P2Si 2, crystallized in the orthorhombic space group P212121 with a = 12.366(2) A?, b = 13.377(2) A?, c = 15.077(4) A?, and Z = 4; P2(i-Pr2NB)2(SiPh 2)·Fe(CO)4, C28H38B2N2O4P 2SiFe, crystallized in the monoclinic space group P21/n with a = 14.403(3) A?, b = 15.550(4) A?, c = 15.632(3) A?, β = 102.07(1)°, and Z = 4; P2(tmpB)2(SiMe2)·Fe(CO)4 crystallized in the monoclinic space group P21/c with a = 11.132(2) A?, b = 32.531(9) A?, c = 17.504(4) A?, β = 92.19(2)°, and Z = 8. The structural features of these cage compounds are compared with data from cages of the type P2(BNR2)3.
