110305-62-9

Upstream product

• 14040-11-0 tungsten hexacarbonyl 
• 110370-69-9 N²,N⁶-bis(diphenylphosphino)pyridine-2,6-diamine 
• 1433219-06-7 [W(N,N′-bis(diphenylphosphino)-2,6-diaminopyridine)(CO)₃H]BF₄ 
• 1433218-99-5 [W(N,N′-bis(diphenylphosphino)-2,6-diaminopyridine)(CO)₃Br]Br 

Downstream Products

• 1433219-06-7 [W(N,N′-bis(diphenylphosphino)-2,6-diaminopyridine)(CO)₃H]BF₄ 

Relevant academic research and scientific papers

A Convenient Solvothermal Synthesis of Group 6 PNP Pincer Tricarbonyl Complexes

The solvothermal synthesis of a series of zerovalent Cr, Mo, and W complexes of the type [M(PNP)(CO)3] featuring PNP pincer ligands based on 2,6-diaminopyridine is described. We demonstrate that the solvothermal synthesis technique presented provides a powerful, simple, and practical synthetic method resulting in high isolated yields in a short time. In particular, Cr and W complexes are not readily accessible via conventional methods. Moreover, this study allows a direct comparison of steric and electronic properties of group 6 metal PNP pincer tricarbonyl complexes.

Synthesis and characterization of hydrido carbonyl molybdenum and tungsten PNP pincer complexes

In the present study the Mo(0) and W(0) complexes [M(PNP)(CO)3] as well as seven-coordinate cationic hydridocarbonyl Mo(II) and W(II) complexes of the type [M(PNP)(CO)3H]+, featuring PNP pincer ligands based on 2,6-diaminopyridine, have been prepared and fully characterized. The synthesis of Mo(0) complexes [Mo(PNP)(CO)3] was accomplished by treatment of [Mo(CO)3(CH3CN)3] with the respective PNP ligands. The analogous W(0) complexes were prepared by reduction of the bromocarbonyl complexes [W(PNP)(CO)3Br]+ with NaHg. These intermediates were obtained from the known dinuclear complex [W(CO) 4(μ-Br)Br]2, prepared in situ from W(CO)6 and stoichiometric amounts of Br2. Addition of HBF4 to [M(PNP)(CO)3] resulted in clean protonation at the molybdenum and tungsten centers to generate the Mo(II) and W(II) hydride complexes [M(PNP)(CO)3H]+. The protonation is fully reversible, and upon addition of NEt3 as base the Mo(0) and W(0) complexes [M(PNP)(CO)3] are regenerated quantitatively. All heptacoordinate complexes exhibit fluxional behavior in solution. The mechanism of the dynamic process of the hydrido carbonyl complexes was investigated by means of DFT calculations, revealing that it occurs in a single step. The structures of representative complexes were determined by X-ray single-crystal analyses.