Elizabeth G. Bent

SILYL- AND GERMYL-DIAZADIPHOSPHETIDINES

Abstract Reaction of the 1,3,2,4-diazadiphosphetidine, trans-[C6H5N(H)P(S)NC6H5]2 with LiR (R = Me, n-Bu) followed by treatment of the resulting dianions with Me3SiCl and Me3GeBr produced trans-[C6H5N(R)P(S)NC6H5]2(R = Me3Si, 2; Me3Ge, 3). Substitution occurs without cis-trans isomerization or significant cleavage of the 1,3,2,4-diazadiphosphetidine ring. 2 and 3 have been characterized by spectral (1H and 31P NMR, IR, and MS) and elemental analytical data. Analogous reactions involving Me3SnCl yield mixtures containing [C6H5N(SnMe3)P(S)NC6H5]2 which could not be isolated or completely characterized.

Triphenylphosphine oxide cocrystallization of a tris(diazaphosphole)molybdenum complex

Abstract Reaction of 1,2-(NH2)2C6H4 with MeP(NEt2)2 yields the new 1,3,2-di-azaphosphole C6H4(NH)2PMe (1). 1 with cycloheptatriene·Mo(CO)3 yields fac-[C6H4(NH)2PMe]3Mo(CO)3 (2), which with Ph3PO from MeCN solution forms the cocrystallate [C6H4(NH)2PMe]3Mo(CO)3·Ph3PO·MeCN (3). New compounds are characterized by spectral data; an X-ray analysis of 3 confirms its structure.

Diastereoselective Formation of Functional Diphosph(III) Azanes

Abstract Diphosph(III)azanes i-PrN[PhP(i-PrNH)](PhPR) (R = Me, Et, Ph, t-Bu) form diastemselectively in reactions of RNH2 with i-PrN[PhP(i-PrNH)](PhPCl). Reactions of 1,3,2-diazaphospholes C6H4(NH)2PR with RPCl2 and RP(Net2)2 (R = Me, Ph) yield i-PrN[PhP(i-RNH)][PhP(RNH)] and C6H4(NH)PRNP(R)X(X=Cl, NEt2), respectively, with modest stereoselection. New diazaphosph (III) azanes are characterized by spectral (31P, 1H, 13C NMR, IR, MS) data and single crystal x-ray analyses of i-PrN[PhP(i-PrNH)][PhP(EtNH)] and C6H4(NH)PEtS(N)P(NEt2)EtS are described.