Reactions of [(Me3SiNCH2CH2)3N]WH with dihydrogen, olefins, acetylenes, carbon monoxide, n-butylisocyanide and azobenzene

Synthesis of Molybdenum Complexes that Contain “Hybrid” Triamidoamine Ligands, [(Hexaisopropylterphenyl-NCH2CH2)2NCH2CH2N-aryl]3-, and Studies Relevant to Catalytic Reduction of Dinitrogen

“…An X-ray structure of 3c was carried out (Figure 4, Tables 1 and 2 2 complexes could be identified in solution, we attempted to isolate only 5c and 5d. Unfortunately, neither 5c nor 5d could be isolated in a sufficiently pure state to pass elemental analyses.…”

“…Some combination of the frontier (two π and one σ) orbitals is sufficient to bind all of the intermediates in a proposed Chart-like reduction cycle. 2 ) has now been confirmed to be extremely slow, with a half-life of ~30 h compared to ~2 h for the parent system under a given set of conditions. 7 ) We believe it is for this reason that [HTBTN 3 N]Mo≡N produces no significant ammonia from dinitrogen (0.06 equiv); the nitride is reduced to ammonia, but the system does not turn over to any significant extent.…”

“…(HIPTNHCH 2 CH 2 ) 2 NCH 2 CH 2 NH 2 The procedure is similar to previous syntheses of symmetric ligands, 4 but utilizes 2.1 equivalents of HIPTBr instead of 3.1 equivalents. A 100 mL toluene solution of Pd 2 (dba) 3 (0.91 g, 0.9 mmol) and rac-BINAP (1.85 g, 2.9 mmol) were stirred with mild heating to preform the active catalyst.…”

“…MoCl 4 (THF) 2 (0.24 g; 0.62 mmol) was then added slowly and the mixture was stirred for one hour, during which time the solution darkened to a deep red. To this red solution 0.30 g (1.8 mmol) of (Me 3 Si) 2 NLi was added and the reaction was stirred for 2 h. The solvent was removed in vacuo and the resulting solid was extracted into pentane. The mixture was filtered through Celite and the solvent removed in vacuo.…”

“…Briefly, 0.76 g (0.63 mmol) of H 3 2d was added to 0.26 g (0.68 mmol) of MoCl 4 (THF) 2 in 50 mL THF. This mixture was stirred for one hour and 0.33 g (1.9 mmol) of (Me 3 Si) 2 NLi was added. After two hours the solvent was removed in vacuo and the resulting solid was extracted into pentane and the extract was filtered through Celite.…”