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Aminochlorophosphanylboranes, (R,N)B(Cl]P(SiMe,), (1 ad) and (R,N)B(Cl)PH, (2a-d), are obtained from elimination reactions between aminochloroboranes and LiP(SiMe3), and LiPH,, respectively. Selected reaction chemistry of (i-Pr,N)B(Cl)[P(SiMe,),] (1 a) with NH,, Me3SiN3, Cr(C0)5 . NMe,, and W(CO), . NMe, is described. The azide (i-Pr,N)B(N,)P(SiMe& (12a) is stable at 25°C; however, thermolysis at 80°C provides a novel six-membered ring compound [(i-Pr,N)BN(SiMe3)P(SiMe3)], (13a). The reaction of (Ph,N)B(Cl)P(SiMe,), (1 b) with LiP(SiMe,), produces the only isolable bis(phosphany1)borane (5 b), while combination of (R,N)B(Cl)PH, with LiPH, . DME yields new diphosphadiboretanes 0 {(R,N)BPH}, (R2N = i-Pr,N, PhzN and tmp = 2,2,6,6-tetramethylpiperidino) and triphosphatriborinanes 7 {(R2N)BPH13 (R2N = (Me,Si),N, MezN and Et2N). T w o 2 I(i-Pr,N)BP(H)B(i-Pr,N)PLi . DME], (8a) and [tmpBP(H)-B(tmp)PLi . DMEI2 (8c) (DME = ethylene glycol dimethyl ether) are also isolated. The results of molecular structure determinations for [(i-PrzN)Bn(SiMe3)P(SiMe3)], (13a), [tmpBPH],

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The reactions of Me(2)SiCl(2), Ph(2)SiCl(2), and Ph(2)GeCl(2) with LiP(H)B(N(i)Pr(2))(2) in a 1:2 ratio and the reaction of Ph(2)SiCl(2) with LiP(H)B(N(i)Pr(2))[N(SiMe(3))(2)] in a 1:2 ratio give good yields of the respective diphosphinosilanes, Me(2)Si[P(H)B(N(i)Pr(2))(2)](2), Ph(2)Si[P(H)B(N(i)Pr(2))(2)](2), Ph(2)Ge[P(H)B(N(i)Pr(2))(2)](2), and Ph(2)Si[P(H)B(N(i)Pr(2))[N(SiMe(3))(2)]](2). These species, when combined with BuLi in a 1:2 ratio, give lithium diphosphinosilanes and -germanes of the general type (DME.Li)(2){[PB(NR(2))(2)](2)ER'(2)}. All of the species have been characterized by spectroscopic methods. The molecular structures of three of the lithio compounds, (DME.Li)(2){[PB(N(i)Pr(2))(2)](2)SiPh(2)} (11), (DME.Li)(2){[PB(N(i)Pr(2))N(SiMe(3))(2)](2)SiPh(2)} (15), and (DME.Li)(2){[PB(N(i)Pr(2))(2)](2)GePh(2)} (13), have been determined by X-ray diffraction techniques. 11 crystallized in the triclinic space group P&onemacr; with a = 11.071(2) Å, b = 14.937(3) Å, c = 18.080(4) Å, alpha = 91.31(3) degrees, beta = 101.23(3) degrees, gamma = 109.95(3) degrees, and Z = 2, and 13 crystallized in the triclinic space group P&onemacr; with a = 11.083(1) Å, b = 14.978(2) Å, c = 18.134(2) Å, alpha = 91.17(1) degrees, beta = 101.43(1) degrees, gamma = 110.05(1) degrees, and Z = 2. 15 crystallized in the monoclinic space group P2(1)/n with a = 11.939(2) Å, b = 24.516(3) Å, c = 21.572(3) Å, beta = 101.52(1) degrees, and Z = 4. The reactions of the lithio compounds were surveyed with R(2)ECl(2) reagents. The metathesis reactions are sluggish, but the 1:1 reaction of (DME.Li)(2){[PB(N(i)Pr(2))(2)](2)GePh(2)} with (t)Bu(2)SnCl(2) gave the four-membered-ring compound The 1:2 reaction of Me(2)(Cl)SiSi(Cl)Me(2) with LiP(H)B(N(i)Pr(2))(2) yielded the (borylphosphino)silane [Me(2)SiP(H)B(N(i)Pr(2))(2)](2).

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