The substituted-exo-phosphine (X = F, NMe2, OCH2CF3) diazaphospholephosphines are exclusively oxidized at this center with either chalcogens (S, Se) or azides to phosphoranodiazaphospholes. Oxidation imparts a dramatic upfield shift of the phosphorus NMR signals and an increase in the (1)J(PC) coupling constants within the ring. (Difluorophosphino)diazaphosphole was also oxidized with selected amines using diethyl azodicarboxylate (DAD) as the coupling agent. Bulky amines (e.g., 2,4,6-tri-tert-butylaniline (mes*)) gave the monomeric iminophosphorane whereas less bulky amines (p-toluidine) formed mostly the cyclic diazadiphosphetidine. The crystal and molecular structure of 4-(difluoro((p-cyanotetrafluorophenyl)imio)-2,5-dimethyl-2H-1,2,3 sigma(2)-diazaphosphole was determined: triclinic, P (1) over bar (No. 2), a = 7.2744(15)Angstrom, b = 10.087(4) Angstrom, c 10.566(2) Angstrom, alpha = 66.62(2)degrees, beta = 77.60(2)degrees, gamma = 78.14(3)degrees, V - 688.81:4) Angstrom(3), Z = 2. Final indices are R-1 = 0.0368 and wR(2) = 0.0968, and for all data, R-1 = 0.0478, wR(2) = 0.1033, and GOF = 1.067. The structure revealed two planar ring systems consisting of the diazaphosphole and the p- tetrafluorophenyl (tfbn) ring with an angle of 26.3 degrees between the rings. The angle about the phosphine imine nitrogen (i.e., P=N-tfbn) is relatively open (141.2(2)degrees) and the P=N bond length is relatively short (1.514(2) Angstrom). (((Trimethylsilyl)imino)(bis(dimethylamio))phosphorano)diazapho sphole gave, with Cp*TiC3, [(eta(5)-C5Me5)TiCl2(N=P(NMe2)(2)(2,5-dimethyl-2H-1,2,3 sigma(2)-diazaphosphol-4-yl))], which was also characterized structurally: monoclinic, P2(1) (No. 4), a = 11.9477(11) Angstrom, b = 8.4757(6) Angstrom, c = 12.7567(11) Angstrom, beta = 108.824(8)degrees V = 1222.7(2) Angstrom(3), Z = 2. Final indices are R1 = 0.0630 and wR(2) = 0.1593, and for all data, R1 = 0.0768, wR(2) = 0.1973, and GOF = 1.081. The Ti-N-P angle of 161.0(5)degrees was large, and the P=N distance (1.592(6) Angstrom and the Ti-N distance (1.781(6) Angstrom) were both slightly shorter than those in similar titanium complexes. The P-N single bond distances between the exo-phosphorus atom and the attached dimethylamino groups were also short (1.649 Angstrom (average)). These short values suggest delocalized bonding character throughout the metalligand framework, possibly a consequence of additional conjugation through the diazaphosphole ring.