Nitrogen atom exchange between molybdenum, tungsten and carbon. A convenient method for N-15 labelingDedicated to Professor Dr. G. Huttner on the occasion of his 65th birthday.

Abstract

The compound (ButO)3W identical to N serves to exchange the nitrogen atoms between nitriles (MeC identical to N and PhC identical to N), itself and (ButO)3Mo identical to N in solution at room temperature.

Synthesis and characterization of a trianionic pincer supported Mo-alkylidene anion and alkyne insertion into a Mo(IV)-C bond to form metallocyclopropene(η2-vinyl) complexes

“…Moore [17], employing the Lewis acid B(C 6 F 5 ) 3 , activate Mo-nitrides toward metathesis with alkynes. This discovery implies that Mnitrides, already known to exchange N-atoms with nitriles [23,24], may be a general entry point to alkyne metathesis catalysts [15,16]. Recently, we proposed that a trianionic pincer ligand may provide the appropriate ligand arrangement for a reactive AM or NACM catalyst [25].…”

Terminal uranium(V)-nitride hydrogenations involving direct addition or Frustrated Lewis Pair mechanisms

“…The 11 gives H 2 , BPh 3 , and 9 in addition to the anticipated NaBPh 4 by-product. The reaction cycle in Fig.…”

“…Since there is an isoelectronic relationship between the M≡N and N≡N triple bonds of metal-nitrides and dinitrogen, N 2 , respectively, the former are fundamentally mechanistically important with respect to Haber Bosch chemistry where they are invoked as intermediates in the cleavage of the latter and conversion to ammonia, NH 3 , by hydrogenolysis with dihydrogen, H 2 6,7 . There has thus been intense interest in the reactivity of metal-nitrides with H 2 , and indeed their use in N-atom transfer reactivity and catalysis more widely [8][9][10][11][12] , but there are few reports of molecular metal-nitrides reacting with H 2 , and indeed activating H 2 in this homogeneous context remains a significant challenge in contrast to heterogeneous Haber Bosch chemistry where H 2 -cleavage is essentially barrier-less 6 . One solution to overcome this hydrogenolysis challenge may be to exploit Frustrated Lewis Pair (FLP) chemistry 13,14 , but so far this has been focussed on M-N 2 complexes 15,16 .…”

Catalytic Isofunctional Reactions—Expanding the Repertoire of Shuttle and Metathesis Reactions

“…With alkyne metathesis finding widespread usage in the synthetic community, the extension of this type of metathesis process to nitriles has garnered attention. In 2003, the group of Chisholm found that W complex 52 could catalyze nitrogen atom exchange between two nitriles (Scheme A) . By using 15 N‐labeled acetonitrile, the formation of 15 N‐labeled benzonitrile from unlabeled benzonitrile could be detected by 15 N NMR spectroscopy.…”