New Silylated Iminophosphorano(amino)phosphines Me₃SiNPPh₂N(R)PPh₂(R = Et,ⁿPr,ⁿBu). Crystal and Molecular Structure of Trimethylsilyliminophosphorano(propylamino)diphenylphosphine Me₃SiNPPh₂N(ⁿPr)PPh₂. Further Oxidative Derivatization with S, Se, and Azides, Titanium(IV) Transmetalation of the Imine, and Syntheses of Rhodium(I), Palladium(II), and Platinum(II) Complexes of These Iminophos

Abstract

Bis(phosphino)amines Ph(2)PN(R)PPh(2) (R = Et, (n)Pr, (n)Bu) react with stoichiometric amounts of trimethylsilyl azide to give the trimethylsilyliminophosphorano(amino)phosphines Me(3)SiN=PPh(2)N(R)PPh(2) (1, R = Et; 2, R = (n)Pr; 3, R = (n)Bu) as crystalline compounds. The structure of 2 has been determined by single-crystal X-ray analysis. (Crystal data for 2: monoclinic, P2(1)/c, a = 10.235(1) A, b = 16.802(2) A, c = 17.075(2) A, beta = 101.05(1) degrees, V = 2882.9(5) A(3), Z = 4.) The structure of 2, which is the first example of an iminophosphoranophosphine with the P(III)-N-P(V)=N skeleton, was solved by direct methods and refined to R = 0.044. Compound 2 readily reacts with elemental sulfur, selenium, or phosphoryl azide to give fully oxidized phosphinimines Ph(2)P(E)N((n)()Pr)Ph(2)P=NSiMe(3) (4, E = S; 5, E = Se; 6, E = NP(O)(OPh)(2)). Compounds 4-6 are very sensitive to moisture and readily undergo desilylation to give the parent phosphinimines Ph(2)P(E)N((n)()Pr)Ph(2)P=NH, which can be isolated as moderately stable crystalline solids. The phosphiniminophosphine 2 and the oxidized phosphinimines (4 and 5) react with CpTiCl(3) to give new nitrogen-bound Ti(IV) derivatives Ph(2)P(E)N((n)Pr)Ph(2)P=NTi(Cp)Cl(2) (10, E = lone pair; 11, E = S; 12, E = Se). Compounds 1-3 readily react with rhodium(I), palladium(II), and platinum(II) complexes to give five-membered metallacycles via phosphorus(III) and imine nitrogen coordination.

N,N′-Bis(ethyldiphenylphosphino)ethylenediamineP,P′-dioxide

“…It is clear that the P V center has accepted much of the lone-pair electron density from the backbone N atom because of the presence of the electronwithdrawing O atom. Similar trends are generally observed in P V -N-P III systems (Balakrishna, Teipel et al, 2001).…”

“…This result is consistent with the reported ligands, Ph (Balakrishna et al, 1999;Zubiri et al, 2002). A similar geometry around the bridging N atoms has also been found in iminophosphorinophosphines (Balakrishna, Teipel et al, 2001). The P O bonds are shorter than those observed in [Ph 2 P(O)] 2 NH [1.519 (2) Å ] and Ph 2 P(S)NHP(O)Ph 2 [1.54 (3) Å ; Slawin et al, 1996)], but agree well with those for Ph 2 P(O)CH 2 N(H)Ph (Priya et al, 2001) and (Zubiri et al, 2002) (both 1.481 Å ).…”

Synthesis, Structure, Reactivity, and Catalytic Activity of C,N‐ and C,N,N‐Orthopalladated Iminophosphoranes

“…The presence of weakly bonded ligands in 4 or 13 seems also to improve the yields, with respect to 1 or 11, at low concentrations of catalyst. On the other hand, a comparison of the different substrates shows that the reactivity of deactivated bromoarenes (p-BrC 6 H 4 CN or pBrC 6 H 4 CHO) is substantially lower for all catalysts than that described for PhI (entries [19][20][21][22][23][24][25][26]. Due to these low conversions, no reactions were attempted with activated bromoarenes or with chloroarenes.…”

Synthesis and derivatization, structures and transition metal (Mo(0), Fe(II), Pd(II) and Pt(II)) complexes of phenylaminobis(diphosphonite), PhN{P(OC6H4OMe-o)2}2

“…The P-N-P angle in the diselenide derivative 4 is larger [127.5(1)°] when compared to the same in the free ligand 1 [116.1(1)°] whereas in the molybdenum complex the P-N-P angle shrinks to 102.4 (2)°due to the formation of a strained four-membered chelate ring. However, the sum of the angles around nitrogen in all these compounds is 359.9°which clearly indicates that the geometry around nitrogen is strictly planar; a characteristic feature of aminobis(phosphines) [5], their dichalcogenides [18,19], diimines [20,21] or metal complexes [22]. The non bonded PÁ Á ÁP separation in complex 5 [2.631(2) Å ] is shorter than that in free ligand 1 [2.868(2) Å ] due to the chelation.…”