Syntheses and Structures of Transition Metal Complexes with Phosphanylphosphinidene Chalcogenide Ligands

Abstract

The reactivity of the phosphanylphosphinidene complex [(DippN)2W­(Cl)­(η2-P-PtBu2)]− (1) toward chalcogens (Ch = Se, S) was studied. Reactions of stoichiometric amounts of 1 with chalcogens in DME yielded monomeric tungsten complexes with phosphanylphosphinidene chalcogenide ligands of the formula tBu2P–P–Ch (Ch = Se (in 2) and S (in 5)), which can be regarded as products of the addition of a chalcogen atom to a PW bond in starting complex 1. The dissolution of selenophosphinidene complex 2 in nondonor solvents led to the formation of a dinuclear complex of tungsten (3) bearing a tBu2P­(Se)–P ligand together with [tBuSe2Li­(dme)2]2 and polyphosphorus species. Under the same reaction conditions, thiophosphinidene complex 5 dimerized via the formation of transient complex 7, possessing a thiotetraphosphane-diido moiety tBu2P­(S)–P–P–PtBu2. The elimination of the tBu2PS group from 7 yielded stable dinuclear tungsten complex 8 with an unusual phosphinidene tBu2P–P–P ligand. The reaction of 1 with excess chalcogen led to the cleavage of the P–P bond in the tBu2P–P ligand and the formation of [(DippN)2­W­(PCh4)]2 2– and [tBuCh2Li­(dme)2]2. The isolated compounds were characterized by NMR spectroscopy and X-ray crystallography. Furthermore, the calculated geometries of the free selenophosphinidenes, tBu2P–P–Se and tBu2P­(Se)−P, were compared with their geometries when serving as ligands in complexes 2 and 3.

Expanding the Utility of β-Diketiminate Ligands in Heavy Group VI Chemistry of Molybdenum and Tungsten

“…Each tungsten center is hexacoordinated in a distorted octahedral coordination environment by the MAD ligand, the two bridging oxides, the new imido ligand and the chloride ligand. The tungsten imido distance of 1.764(12) Å for W1–N40 is substantially longer as in the terminal oxo complexes reported here (between 1.65–1.69 Å) but matches well with previously reported Dipp-imido tungsten complexes (1.73–1.77 Å in average). ,,,,, The oxo bridge is asymmetric with W1–O10 distances of 1.801(10) and 2.220(11) Å. These distances are slightly longer compared to the tungsten­(V) dimer 16 , which is expected considering the lack of a d 1 –d 1 W V –W V interaction.…”

Multifunctionalized Metal Chalcogenides and Their Roles in Catalysis and Biomedical Applications

“…With the development of designed techniques and allowing reasonable control of the response characteristics, the synthesis of nanomaterials with attractive shape and measure is now possible. Additionally, the local ligands have systematically taken away or reintroduced and the surface ligands have changed as needed [32] . Metal chalcogenides included a range of substances with different oxidation states.…”

“…Additionally, the local ligands have systematically taken away or reintroduced and the surface ligands have changed as needed. [32] Metal chalcogenides included a range of substances with different oxidation states. So, in addition to measuring and shaping, oxidation states have adjusted for better electrocatalytic performance.…”