Syntheses and Structures of P-Anilino-P-chalcogeno- and P-Anilino-P-iminodiazasilaphosphetidines and Their Group 12 and 13 Metal Compounds

Abstract

The P-anilino-P-chalcogeno(imino)diazasilaphosphetidines [Me(2)Si(mu-N(t)Bu)(2)P=E(NHPh)] (E = O (3), S (4), Se (5), N-p-tolyl (6)) were synthesized by oxidizing the P-anilinodiazasilaphosphetidine [Me(2)Si(N(t)Bu)(2)P(NHPh)] (2) with cumene hydroperoxide, sulfur, selenium, and p-tolyl azide, respectively. The lithium salt of 4 reacted with thallium monochloride to produce ([Me(2)Si(mu-N(t)Bu)(2)P=S(NPh)-kappaN-kappaS]Tl)(7), which features a two-coordinate thallium atom. Treatment of 4-6 with AlMe(3) gave the monoligand dimethylaluminum complexes ([Me(2)Si(mu-N(t)Bu)(2)P=E(NPh)-kappaN-kappaE]AlMe(2)) (E = S (8), Se (9), N-p-tolyl (10)), respectively. In these complexes the aluminum atom is tetrahedrally coordinated by one chelating ligand and two methyl groups, as a single-crystal X-ray analysis of 8 showed. A 2 equiv amount of 4-6 reacted with diethylzinc to produce the homoleptic diligand complexes ([Me(2)Si(mu-N(t)Bu)(2)P=E(NPh)-kappaN-kappaE](2)Zn)(E = S (11), Se (12), N-p-tolyl (13)). A crystal-structure analysis of 11 revealed a linear tetraspirocycle with a tetrahedrally coordinated, central zinc atom.

Syntheses and crystal structures of mono- and bi-metallic zinc compounds of symmetrically- and asymmetrically-substituted bis(amino)cyclodiphosph(V)azanes

“…While the zinc-nitrogen and zinc-oxygen bonds are identical in both compounds, the shorter ethyl-zinc bond of the sulfur analogue may reflect the lesser steric crowding in this compound. The Zn-S bond (2.4480(12) A) is somewhat longer than that in {[Me 2 Si(l-N t Bu) 2 P@S(NPh)] 2 Zn} [33], while the Zn-Se (2.5398 (18) A) bond is almost identical in length to that in a tetracoordinate zinc complex having two acyclic amino(seleno)phosphoranate ligands [27].…”

“…Because we recently reported the X-ray structure analysis of the related {[Me 2 Si(l-N t Bu) 2 P@S(NPh)] 2 Zn} [33], which shows a tetrahedral zinc atom chelated by two P@S(NPh) moieties, it may be assumed that 6 is a similar trispirocycle. The structure of 6 is an indication that the product of the reaction between [(PhHN)S@P(l-N t Bu) 2 P@S(NHPh)] and diethylzinc is, indeed, an oligomer or a polymer.…”

N-versus O-silylation in cis-[(tBuHN)OP(μ-NtBu)2PO(NHtBu)] and [Me2Si(μ-NtBu)2PO(NHPh)]. Solid-state structures of their silylation products, of co-crystalline cis-[(tBuHN)OP(μ-NtBu)2PO(NHtBu)], and of {[Me2Si(μ-NtBu)2PO(N(SiMe3)Ph)]VCl3}

“…The heterocycles [Me 2 Si(l-N t Bu) 2 P@O(NHPh)] [38] and cis-[( t BuHN)O@P(l-N t Bu) 2 P@O(NH t Bu)] [15] were synthesized according to published procedures.…”

Inorganic Heterocyclic Bis(phosphines): Syntheses and Structures of a 1,2-Bis(diazasilaphosphetidino)ethane and Its Nickel, Molybdenum, and Rhodium Complexes

“…[63][64][65] The Mo-P bond lengths in the structurally characterized H and J, being 2. 48(1) and 2.480(2) Å, respectively, are similar to those of cis-[(dppe)Mo(CO) 4 ] (2.497(2) Å), 68 but the coordination chemistry of these heterocycles as P-donors turned out to be more complex than had been anticipated. This was partly so because cyclodiphosph(III)azanes can undergo cis-trans isomerismsproperties that are undesirable in a spectator ligandsbut more importantly because these These results can be understood in terms of the electronic structure of these heterocyclic phosphines.…”

“…Both the slightly asymmetrical P-N bonds (1.7278(16) Å) and the symmetrical Si-N bonds (1.7139(17) Å) have similar lengths as those in related diazasilaphosphetidines. [45][46][47][48] To assess the structural and electronic properties of bdpe, we synthesized nickel(II) and molybdenum(0) derivatives for which bis(diphenylphosphino)ethane (hereafter dppe) complexes are known. While 2 bears much closer resemblance to the cyclic organic phosphines A and B, very limited structural information on metal complexes of these ligands, other than rhodium, is available.…”