Synthesis and Characterization of (2,4,6-Trimethylphenylimido)molybdenum Complexes. X-ray Crystal Structures of (L_OEt)Mo(Nmes)₂Cl, (L_OEt)Mo(Nmes)Cl₂, and MoCl₃(Nmes)(depe) (mes = 2,4,6-Trimethylphenyl, L_OEt= (η-C₅H₅)Co{P(O)(OEt)₂}₃, depe = Et₂PCH₂CH₂PEt₂)

Abstract

The bis(imido) complex MoCl(2)(Nmes)(2)(dme) (1) (mes = 2,4,6-trimethylphenyl, dme = 1,2-dimethoxyethane) has been used as the starting material for the preparation of the compounds (L(OEt))Mo(Nmes)(2)Cl (2) (L(OEt) = (eta-C(5)H(5))Co{P(O)(OEt)(2)}(3)) and Mo(Nmes)(2)(acac)(2) (5), as well as for the synthesis of the mixed oxo-imido MoCl(2)(Nmes)(O)(dme) (6), the latter reaction involving conproportionation of 1 and MoCl(2)(O)(2)(dme). Similarly, the paramagnetic mono(imido) species Mo(Nmes)Cl(3)(dme) (11) can also be obtained from 1 by interaction with MoCl(4)(THF)(2) (THF = tetrahydrofuran) in refluxing dme. Compounds 6 and 11 are suitable sources for the synthesis of other diamagnetic mixed oxo-imido and paramagnetic mono(imido) compounds, respectively. Three of the newly synthesized complexes, namely, (L(OEt))Mo(Nmes)(2)Cl (2), (L(OEt))Mo(Nmes)Cl(2) (12), and MoCl(3)(Nmes)(depe) (14) (depe = Et(2)PCH(2)CH(2)PEt(2)) have been characterized by X-ray crystallography.

A Terminal Nitride‐to‐Phosphide Conversion Sequence Followed by Tungsten Phosphide Functionalization Using a Diphenylphosphenium Synthon

“…With subsequent intermetal exchange of P and O ligands, the known oxidoniobium complex 2 would be generated as well as a new terminal phosphide complex [PW{N( i Pr)Ar} 3 ] ( 5 ). Several examples of installing multiply bonded ligands (oxide, imide, and alkylidene) by intermetal ligand exchange have been reported;7–16 herein, we extend this concept to the terminal phosphide functional group.…”

Oxo-Bridged (Haloarylimido)[tris(3,5-dimethylpyrazolyl)borato]- molybdenum(V) Complexes: Crystal Structures of Geometric Isomers of [MoTp*(O)Cl](μ-O)[MoTp*(Cl)(≡NC6H4Br)]

“…There are two interesting features related to the crystal structures of 1a and 1b. Firstly, there is an Mo-N-R linkage which could be considered as near-linear with Mo(1)-N(1)-C(1) bond angles of 156.19 (17) • in 1a and 176.0(4) • in 1b, respectively. These values are in accord with the range of 160 -180 • for linear angles suggested by Dehnicke [27].…”

Synthesis, characterization and electrochemical behavior of oxo-bridged (arylimido)[tris(3,5-dimethylpyrazolyl)borato] molybdenum(V) complexes

“…Organo-imido complexes of Mo(V) and Mo(VI) can be prepared by a wide range of methods that often make use of organic compounds as the imido transfer reagent [3,4]. There are several molybdenum imido compounds [5][6][7][8][9][10] and a number of related mixed terminal oxo-imido compounds have previously been reported, for instance [MoTp*(O)Cl(NR)] (R = 4-tolyl and C 6 H 4 NMe 2 -4) [11], [MoCl 2 (Nmes)(O)(bipy)] (mes = 2,4,6-trimethylphenyl) [12] and [TpMo(CH 2 C(Me)(2)Ph)(NAr)(O)] (Ar = 2,6-i-Pr-2-C 6 H 3 , Ph = C 6 H 5 ) [13], but limited information is available for transition metal compounds containing both imido and hydrotris(pyrazolyl)borate type ligands [11,[14][15][16][17][18][19][20][21]. Although a number of systems involving l-ligation in the presence of terminal imido groups have previously been reported [22][23][24][25][26], the chemistry of compounds having both arylimido and l-oxo group in the presence of tris(pyrazolyl)borate co-ligand has not been studied in detail.…”