Reversible addition of carbonyl compounds to parent imido complex: preparation and crystal structures of trans-{Mo(NH)(OTf)(syn-Me₈[16]anes₄)}OTf and trans-{Mo[NC(OH)RR′](OTf)(syn-Me₈[16]aneS₄)}OTf (RR′Me; RH, R′Ph)

Abstract

Reversible C-N bond formation of a parent imido complex trans-{ Mo(NH)(OTf) aneS4)}0Tf 1 proceeds through addition of acetone and benzaldehyde to give a-hydroxyalkylimido complexes trans-{Mo[NC(OH)RR'](OTf)(syn-Me8[16]aneS4)}0Tf (2; R=R'=Me, 3; R=H, R'=Ph); the structures of two imido complexes 1 and 3 as well as trans-Mo(N--+BPh3)(0Tf) aneS4) 4 obtained by treating 1 and 2 with NaBPh4 were elucidated by X-ray diffraction study.

Synthesis and Reactivity of [Tp‘(CO)(PhC⋮CMe)WNPh]+ (Tp‘ = Hydridotris(3,5-dimethylpyrazolyl)borate)

“…Nucleophilic reactivity at nitrogen, while more prevalent for bent nitrenes, has been observed for both bonding modes. − Nucleophilic nitrenes of zirconium have been used as reagents for the hydroamination of alkynes and in imine−azide metathesis reactions .…”

Conformational analysis of 14- and 16-membered unsaturated oxa, thia, and selena macrocyclic ligands

“…Similar arguments were invoked to explain the anti conformation of (10b)Mon(CN)2 VAZSOE, in which the Mo atom lies strictly in the $4 plane [80]. However, while the crystal structure of (10b)MoIV(phaB)(N) HAYLIC shows the anti conformation, the syn predominates in CDCls solution [81]. This demonstrates the finely balanced energetics of the Mo(10b) system; the precise electronic properties of the axial ligands and effects of crystal packing are probably critical in determining the solidstate conformation.…”

“…The small energy differences are apparent in solution, where several conformers have been shown to be present in some instances [58,59,81]. Thus, the solid-state conformation is liable to be influenced by intermolecular interactions.…”

Synthesis, Molecular Structure and Reactivity of a Calix[4]arene Monomethyl Ether Supported Nitridomolybdenum Complex

“…Whereas the formation and the chemistry of complexes with an [ReϵN-EX 3 ] (E = group 13 element) linkage has been rather thoroughly investigated, mainly by the groups of Strähle and Abram, [16] there are few known examples of similar complexes of group 6 metals. With the exception of the complex [trans-Mo(N-BPh 3 )(OTf)(anti-Me 8 [16]aneS 4 )] (Me 8 [16]aneS 4 = 3,3,7,7,11,11,15,15-octamethyl-1,5,9,13-tetrathiacyclohexadecane, OTf = SO 3 CF 3 ) published by Yoshida et al, [17] this type of compound is, to the best of our knowledge, unknown in group 6 chemistry. Therefore we were interested in the adduct formation of complex 1 with group 13 tris(halide) and tris(alkyl) compounds.…”