SYNTHESIS OF MONOPHOSPHORUS AND DIPHOSPHORUS PHOSPHAZANE OLIGOMER POLYMER PRECURSORS

Reactions of RP(NEt2)2 (R = Me, Et, t-Bu, Ph) with 1,2-(NH2)2C6H4 (0.8:1.0 ratio) yield the 1,3,2-diazaphospholes C6H4-(NH)2PR [R = Me (4), Et (5), t-Bu (6), Ph (7)]. At higher ratios (2:1) the diphosphazanes C6H4(NH)PRNP(NEt2)R [R = Me (9), Et (10), t-Bu (11), Ph (12)] form. 4–7 and 9–12 were characterized in solution by spectral data; 9-12 form as mixtures of diastereomers. 4 and 10 upon reaction with S8 are converted to C6H4(NH)2P(S)Me (8) and two diastereomers of C6H4-(NH)PEt(S)NP(NEt2)(S)Et (13a, b). 4 with cycloheptatriene-Mo(CO)3 forms the derivative complex fac-[C6H4-(NH)2PMe]3Mo(CO)3 (15). 15 crystallizes from MeCN with Ph3PO as the cocrystallate fac-[C6H4(NH)2PMe]3Mo(CO)3-3Ph3PO·MeCN (16). X-ray analyses of 13a and 16 were carried out. 13a: monoclinic, Pn, a = 8.561 (3) Å, b = 7.705 (3) Å, c = 14.036 (4) Å, β = 95.97 (2)°, V= 920.8 (5) Å3, dcalc = 1.304 g/cm3, 2=2. 16: monoclinic, P21, a = 12.869 (5) Å, b = 16.312(5) Å, c = 18.853 (7) Å, β = 108.15 (3)°, V= 3761 (2) Å3, dcalc = 1.322 g/cm3, Z = 2. 16 contains three Ph3PO molecules H-bonded to the six N–H bonds of the diazaphosphole rings in an approximate 3-fold symmetry pattern. © 1990, American Chemical Society. All rights reserved.