Stoichiometric molecular single source precursors to cobalt phosphides

Multimetallic Catalysis Based on Heterometallic Complexes and Clusters

“…Severe activation conditions may lead to segregation of the different metals and jeopardize synergistic interactions. The use of carbonyl clusters is particularly appropriate, also because the CO ligands are cleanly and irreversibly eliminated, in contrast to, for example, phosphines that may become the source of desirable or undesirable phosphide phases. , It is generally observed that the use of well-defined bimetallic molecular precursors leads to metal particles of much better controlled size and composition than those obtained from mixtures of monometallic salts, because of the close proximity of the atoms in the precursors and the existence of metal–metal bonding. The large number of experimental parameters involved in catalytic studies (solvent, temperature, pressure), the nature of the support, the impregnation method used, the thermal decomposition, and activation procedures of the catalysts all need to be considered, and making comparisons between results from different research groups is very difficult, if not meaningless.…”

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands

“…The influence of the Co/P ratio on the nature of the nanoparticles was examined by thermal treatment of bulk samples of the clusters [Co 4 (CO) 10 (μ-DPPA)] (Co/P = 2) and [Co 4 (CO) 8 (μ-DPPA) 2 ] (Co/P = 1) used as single-source precursors. Whereas the former led to Co 2 P only, the latter gave a mixture of CoP (major) and Co 2 P …”

“…93,94 The latter ligand was characterized in solution, by its 31 15). These complexes are diamagnetic in solution, with singlet resonances in their 31 P NMR spectra at 42.9 (197) and 45.4 (198) ppm. After activation with AlEtCl 2 , these complexes were found to be active catalysts for the selective oligomerization of ethylene (see section 13.2).…”

“…196 The influence of the Co/P ratio on the nature of the nanoparticles was examined by thermal treatment of bulk samples of the clusters [Co 4 (CO) 10 (μ-DPPA)] (Co/P = 2) and [Co 4 (CO) 8 (μ-DPPA) 2 ] (Co/P = 1) used as single-source precursors. Whereas the former led to Co 2 P only, the latter gave a mixture of CoP (major) and Co 2 P. 197 Through elegant studies by 31 P CP/MAS spectroscopy, Blumel and colleagues studied the immobilization of the isolated Ni(0) dicarbonyl complex 274 containing the Nalkoxysilyl DPPA-type ligand 259 onto neutral and rigorously dried alumina and observed the exclusive formation of the supported catalyst 274−{Al 2 O 3 }. 111 No uncomplexed phosphine nor substantial amount of side products were detected, and the procedure was then applied to the analogous complex 275 containing ligand 261, in which the flexible n-propyl linker between the PNP moiety and the alkoxysilyl group of 259 has been replaced by a rigid aromatic phenyl.…”

Mercurophilic interactions in heterometallic Ru-Hg carbonyl clusters

“…Among the different classes of inorganic and organometallic compounds displaying metallophilicity, some interesting examples have been also reported for heterometallic carbonyl clusters [20][21][22][23][24][25][26][27][28]. In addition, heterometallic clusters can be employed for the activation of small organic molecules [29][30][31][32][33][34][35][36][37][38], for applications in homeogeneous catalysis and as precursors of metal nanoparticles and heterogeneous nanostructured catalysts [39][40][41][42][43][44][45][46][47][48][49][50][51][52].…”