Facile Synthesis and Molecular Structure of [Ni(PPh2NHPh)4]

Abstract

NiCl 2´6 H 2 O readily reacts with PPh 2 NHPh in the presence of zinc dust to yield the homoleptic nickel(0) tetrakis-phosphine complex [Ni(PPh 2 NHPh) 4 ] (1). 1 crystallises triclinic P1 (no. 2), with a = 14.656(1), b = 17.124(2), c = 17.424(1) A Ê , a = 95.998(1), b = 111.845(1), c = 111.402(1)°, V = 3630.04(5) A Ê 3 , Z = 2, R values [I > 2r(I)]: R1 = 0.0554, all data: wR2 = 0.1720. The nickel atom is coordinated in a distorted tetrahedral fashion by four phosphorus atoms, resembling a compressed tetrahedron along one of the noncrystallographic S 4 axes.

Main-group and transition-metal complexes of bis(phosphinimino)methanides

“…9 In transition-metal chemistry this concept is today sometimes referred as ''post-metallocene'' chemistry. [11][12][13] In this context ligands that contain P-N units such as phosphoraneiminates (R 3 PN) À , [14][15][16][17][18] phosphinimines (R 2 PNR 0 ), [19][20][21][22][23] diphosphanylamides (R 2 PNPR 2 ) À , [24][25][26][27] and iminophosphonamides ((R 2 P(NR 0 ) 2 ) À , [28][29][30][31][32] attracted much attention in main-group and transition-metal chemistry.…”

(R/S)A2- or (R,S/S,R)p,p‘-[Pd(κ2-P,P-{P(OC6H3But2-2,4)2N(Me)C(O)N(Me)PPh2}Cl2]: Chirality Created by Ring Tilting

“…The phosphorus NMR spectrum displays no coupling between the two different phosphorus centers. As dynamic behavior is known in tetrahedral nickel(0) complexes of similar ligands, low-temperature NMR ( 1 H and 31 P{ 1 H}) was performed to find out whether the absence of P−P coupling in the NMR spectrum of 1 is due to the palladium or dynamic behavior of the P−Pd bonds. As expected, the spectra at 213 and 300 K were identical except for a small temperature-dependent shift.…”

Role of Bis(phosphinimino)methanides as Universal Ligands in the Coordination Sphere of Metals across the Periodic Table

“…Some of the resulting complexes were successfully applied in homogeneous catalysis. − Due to the 31 P nucleus with S = 1/2, which has a 100% abundance, P–N ligands and their corresponding complexes in general are suitable for NMR studies. The use of various ligands with P–N units, such as phosphoraneiminates (R 3 PN) − , − phosphinimines (R 2 PNR′), − diphosphanylamides (R 2 PNPR 2 ) − , − and iminophosphonamides (R 2 P­(NR′) 2 ) − , − already evidenced their efficiency and utility to stabilize main-group, transition, rare-earth, and actinide metal ions through the multiple coordinating sites. Furthermore, P–N ligands with added chalcogen or boron atoms bonded to the phosphorus atoms are also known as ligands in main-group chemistry. − …”