Formation and structure of a quadruply-iodo-bridged complex of dimolybdenum(III,IV), [(Cp*Mo)₂(µ-l)₄]l₃(Cp*=η⁵-C₅Me₅) and its reversible oxidation and reduction

Abstract

The mixed-valence quadruply-iodo-bridged [ ( C p * M ~) ~( p -l ) ~] l ~ has been crystallographically characterized; its cyclic voltammogram shows reversible oxidation and reduction processes and suggests that the [ ( C ~* M o ) ~( p -l ) ~] *( n = 0, 1, 2) series of complexes is isostructural.

Halogenation of Diphosphorus Complexes

“…The one at −101.1 ppm could not be undoubtedly assigned, but due to its chemical shift, one can assume that it belongs to a small molecule in which the P nucleus is surrounded by more than three halogens such as undissociated PBr 5 and is therefore denoted as PBr x . The formation of PBr 3 suggests that part of 1 is completely brominated to PBr 3 and probably CpMoBr 4 or [(CpMo) 2 (μ-Br 4 )] are formed . The reaction of 1 with Br 2 leads to the formation of the same products as with PBr 5 .…”

Organometallic Halides: Preparation and Physical and Chemical Properties of Tris[(η-pentamethylcyclopentadienyl)dichlorovanadium], [(η-C5Me5)V(μ-Cl)2]3

“…However, most (η-C 5 R 5 )MXY compounds are dimeric. A few, for example [(η-C 5 Me 4 Et)V] 2 (μ-Br) 4 , ,,, {[(η-C 6 H 3 Me 3 )Nb] 2 (μ-I) 4 } n + ( n = 0, 1), [(η-C 5 Me 5 )Ta] 2 (μ-Br) 4 , [(η-C 5 Me 5 )W] 2 (μ-Cl) 4 , and several [(η-C 5 R 5 )Mo] 2 (μ-X) 4 (X = halogen), ,,,− adopt the structure 2a . The majority adopt the structure 2b , for example, [(η-C 5 H 2 (SiMe 3 ) 3 )TiCl(μ-O)] 2 , [(η-C 5 Me 5 )MX(μ-Cl)] 2 (X = Cl; M = Cr, ,, Re, Ru, , Rh, Ir; X = Me; M = Cr , ), [(η-C 5 R 5 )M(O)(μ-O)] 2 (M = Cr, Mo ), and [(η-C 5 R 5 )M(E 1 )(μ-E 2 )] 2 (M = Mo, W; E 1 = O, S; E 2 = S, Se − ).…”

Monocyclopentadienylmolybdenum(iii) Chemistry

“…Its cyclic voltammogram shows reversible one-electron reduction and oxidation processes, thus providing persuasive evidence for the existence of a tetra-iodo bridge Mo( 111) dimer. 44 The analogous reaction with HBr also shows evidence for the intermediate formation of the exchange product (PMe,/EPR test), but again a different product is ultimately obtained. This has NMR properties similar to those of the I, salt obtained as described in eq 16, but recrystallization of this material has afforded single crystals of the Mo(IV) derivative [ C~* M O B~, ] , .~~…”