Unusual reaction of a tungsten alkylidyne complex with water. Formation, characterization, and crystal structures of oxo trimers

Abstract

O) 3 ]·2benzene-d 6 (3·2benzene-d 6 ), respectively, each containing two alkyl ligands per W atom. This is in contrast to the dimer W 2 O 2 (-O)(CH 2 CMe 3 ) 6 , containing three alkyl ligands per W atom, from the previously reported reaction of the alkyl alkylidyne analog W(CH 2 CMe 3 ) 3 -(CCMe 3 ) with H 2 O. In the reaction of 1 with D 2 O in THF, an unstable intermediate W 2 O 2 (-O)(CD 2 SiMe 3 ) 2 (CH 2 CMe 3 ) 4 (4-d 4 ) was identified. Kinetic studies of the reactions of 1 with excess H 2 O and D 2 O in THF-d 8 , yielding 4 and 4-d 4 , respectively, give a kinetic isotope effect (KIE) of 3.46(3) at 298(1) K, suggesting that the disappearance of 1 is a rate-determining step. alkylidyne, water, oxo complexes, kinetic isotope effectMany early transition metal complexes are moisturesensitive, and reactions of metal complexes with water have been used to make metal oxides [1][2][3] in, e.g. microelectronic industry. Such reactions with water have attracted much attention [4][5][6][7][8][9][10][11][12][13]. Schrock, Lippard and coworkers reported the formation of the dimer W 2

Hydrolysis of organometallic and metal–amide precursors: synthesis routes to oxo-bridged heterometallic complexes, metal-oxo clusters and metal oxide nanoparticles

“…84,85 Studies of the hydrolysis of organo-transition metal complexes are uncommon; however, isolated examples of reactions of complexes containing metal−carbon multiple bonds have been reported, for example, the reactions of W(≡E t Bu)(CH2 t Bu)3 (E = C, Si) and Mo(=CH t Bu)(CH2 t Bu)2(≡N t Bu), with excess water. [86][87][88][89] In such examples, partial hydrolysis occurs with enhanced reactivity at the M−C/N multiple bonds. The products retain some single M−C bonds highlighting the relative stability of M−C bonds in heavier transition metal complexes, where significant covalency is present.…”

Extension of Surface Organometallic Chemistry to Metal–Organic Frameworks: Development of a Well-Defined Single Site [(≡Zr–O−)W(═O)(CH2tBu)3] Olefin Metathesis Catalyst

“…Indeed Xue et al showed that 1 undergoes readily hydrolysis with the formation of a stable dinuclear (Np 3 W=O)-O-(Np 3 W=O) complex without further neopentane release. 96 Moreover Schrock et al had previously reported the reaction of the W(≡C t Bu)(CH 2 t Bu) 3 with water and showed that water could transfer hydrogen to the W≡C resulting in a W=O and a W-CH 2 bond leaving the oxidation state of W unchanged and giving very stable species similar to W4A. 83 The presence of W4A species is also confirmed by different solid state NMR approaches.…”

From China to the world: Science China Chemistry celebrates the International Year of Chemistry

“…The work here calls for particular attention to solvent choice in the synthesis of mesoporous materials [22]. As part of their studies of d 0 metal complexes with water and oxygen and alkylidyne and alkylidene complexes, Brenda Dougan and Zi-Ling Xue investigated the reaction of water with W(CH 2 CMe 3 ) 3 (CSiMe 3 ), and found the reaction yields W 3 O 3 (=O) 3 (CH 2 CMe 3 ) 6 as either a THF or D 2 O adduct containing two neopentyl ligands per W atom in the trimer (Figure 7) [20].…”

“…Graphic abstract of the paper by Dougan and Xue [20]. complexes bearing monoanionic ancillary ligands and their use as homogeneous catalysts in polymerization of various olefins [37].…”

“…Among the authors are many female scientists ( Figure 2). One Feature Article [11], seven Reviews [1218], two Communications [19,20], twelve Articles [2132] and seven News & Comments [10, 3338] were published in the special IYC issue. These papers explored fundamental chemistries and chemical bases of life processes, as well as their potential applications.…”