Synthesis and Crystal Structure of Unprecedented Phosphine Adducts of d¹-Aryl Imido−Vanadium(IV) Complexes

Abstract

The reaction of the imido precursor [V(NAr)Cl(2)](n)() (1) (Ar = 2,6-i-Pr(2)C(6)H(3)) with 3 equiv of PMe(2)Ph yields the monomeric complex [V(=NAr)Cl(2)(PMe(2)Ph)(2)] (2). Reacting 1 with 1.5 equiv of dmpe or 1 equiv of dppm affords the dimeric complexes [V(=NAr)Cl(2)(dmpe)](2)(mu-P,P'-dmpe) (3) and [V(=NAr)Cl(2)(dppm)](2) (4), respectively. Complexes 2-4 have been fully characterized by spectroscopic methods, magnetism studies, and X-ray crystallography.

Titanium–Imido Complexes with Pendant Groups – Synthesis, Characterization, and Evaluation of Their Role as Precatalysts for Ethylene Polymerization

“…The N imido –Ti–Cl angles are in the range 107–115°, and theN imido –Ti–N angles are in the range 94–100°. The distances and angles associated with the titanium center and the ligands are comparable to those found in other [M(=NR)Cl 2 (NHMe 2 ) 2 ] complexes (M = Ti,24,25,27V22,23). The complexes exhibit a short Ti–N imido distance of 1.6979(16) for O 1 , 1.700(2) for S 1 , and 1.701(3) Å for S 2 , and the imido linkage is almost linear [Ti–N imido –C ipso 175.72(14), 174.6(2), and 166.9(2)° in O 1 , S 1 , and S 2 , respectively].…”

A General and Facile One‐Step Synthesis of Imido–Titanium(IV) Complexes: Application to the Synthesis of Compounds Containing Functionalized or Chiral Imido Ligands and Bimetallic Diimido Architectures

“…[5] We have further demonstrated that various aryl-imido groups could be very conveniently introduced by a one-pot synthesis from V(NMe 2 ) 4 , the corresponding aniline, and chlorotrimethylsilane. [21] We have also studied the coordination chemistry of these new complexes with N-or P-donor neutral ligands, [21,22] and the results suggest that imido compounds of this type could lead to a large variety of vanadium coordination compounds. Furthermore, some of these imido-vanadium species have been shown to possess catalytic activities in olefin polymerization [5] and in alkyne hydroamination.…”

A study on the electronic effect of para substituents in the aryloxy ring of the hydrazone ligands on the vanadium centre in a family of mixed-ligand [VVO(ONO)(OO)] complexes

“…In vanadium chemistry, two commonly occurring motifs, viz., VO 2+ and VO 3+ , have attracted special attention after the discoveries of their involvements in many biochemical and physiological processes such as haloperoxidation [1][2][3][4], phosphorylation [5], vanadium nitrogenases [6], a-olefin polymerization [7][8][9][10][11], insulin mimicking [12][13][14][15][16][17][18][19][20][21], anticancer [22,23], antitumour [24] and antifungal/antibacterial [25] activities. Due to hard acidic nature of these two motifs, they have strong affinity towards the hard basic O, N-donor ligands.…”

“…respectively, while the aromatic protons H(16), H(17), H(18) and H(25) appear as doublet of doublets respectively at d7.43, d7.13, d7.47 and d 7.61 p.p.m. Other aromatic protons H(7,9,27) appear as a multiplet at ca. d7.29-d7.38 p.p.m.…”