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• W2025794018 startingPage "2903" @default.
• W2025794018 abstract "Reaction of the niobium diphosphine compound [NbCp(NAr)(PMe3)2] (Ar = 2,6-C6H3Pri2) with HSiMe2Cl gives the formally d2 silylamido derivative [NbCp{η3-N(Ar)SiMe2-H}Cl(PMe3)] 6. X-Ray diffraction and NMR studies of this compound show that it has a stretched β-agostic Si–H → Nb interaction. Reaction of the related precursor [NbCp(NAr′)(PMe3)2] (Ar′ = 2,6-C6H3Me2) with HSiMe2Cl gives an isomeric structure [NbCp{η3-N(Ar′)SiMe2-H}(PMe3)(Cl)] 7 differing from 6 in that the phosphine rather than chloride lies trans to the co-ordinated Si–H bond. A preliminary X-ray study and large 1J(Si–H) coupling constant of 116 Hz suggest that this compound is best described as an unstretched β-agostic (Si–H⋯M) d2 silylamide complex. Reaction of the tantalum diphosphine compound [TaCp(NAr)(PMe3)2] with HSiMe2Cl affords the d0 silylhydride derivative [TaCp(NAr)(H)(SiMe2Cl)(PMe3)] 8 which, according to an X-ray diffraction study and NMR data, has an interligand hypervalent interaction (IHI) between the silyl and hydride ligands. Reactions of 6 and 8 with Me3SiX (X = I, OTf) lead to the corresponding iodido and triflate derivatives [NbCp{η3-N(Ar)SiMe2-H}X(PMe3)] (X = OTf 11 or I 12) and [TaCp(NAr)(H)(SiMe2X)(PMe3)] (X = OTf 14 or I 15). Reaction of 8 with AgOTf gives [TaCp(NAr)(PMe3)2Cl]OTf 13, the crystal structure of which has been determined. Density functional theory calculations on models of the compounds 6 and 7 showed that the experimental geometries are only correctly reproduced when the phosphine ligands are adequately modelled. The extent of oxidative addition of the Si–H bond to the metal in 6 mainly depends on the basicity of the phosphine ligand. With PH3 in place of PMe3 the calculated structures are better described as silanimine-hydrido derivatives. The formation of isomeric type 6versus7 is determined by an interplay of the steric and electronic effects of the ligand environment." @default.
• W2025794018 created "2016-06-24" @default.
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• W2025794018 date "2001-01-01" @default.
• W2025794018 modified "2023-10-16" @default.
• W2025794018 title "Surprising diversity of non-classical silicon–hydrogen interactions in half-sandwich complexes of Nb and Ta: M–H ⋯ Si–Cl interligand hypervalent interaction (IHI) versus stretched and unstretched β-Si–H⋯M agostic bonding†" @default.
• W2025794018 cites W162134388 @default.
• W2025794018 cites W1965949497 @default.
• W2025794018 cites W1966182479 @default.
• W2025794018 cites W1968218307 @default.
• W2025794018 cites W1972955843 @default.
• W2025794018 cites W1978665117 @default.
• W2025794018 cites W1983300404 @default.
• W2025794018 cites W1987134431 @default.
• W2025794018 cites W1988029044 @default.
• W2025794018 cites W1991569872 @default.
• W2025794018 cites W1994884720 @default.
• W2025794018 cites W1997264071 @default.
• W2025794018 cites W1997959560 @default.
• W2025794018 cites W2001554124 @default.
• W2025794018 cites W2004933104 @default.
• W2025794018 cites W2006395860 @default.
• W2025794018 cites W2007223165 @default.
• W2025794018 cites W2009715252 @default.
• W2025794018 cites W2012656110 @default.
• W2025794018 cites W2015947358 @default.
• W2025794018 cites W2017254179 @default.
• W2025794018 cites W2017960523 @default.
• W2025794018 cites W2030687437 @default.
• W2025794018 cites W2031294284 @default.
• W2025794018 cites W2034232281 @default.
• W2025794018 cites W2034571446 @default.
• W2025794018 cites W2035477180 @default.
• W2025794018 cites W2036146015 @default.
• W2025794018 cites W2039028682 @default.
• W2025794018 cites W2040371083 @default.
• W2025794018 cites W2040921452 @default.
• W2025794018 cites W2041521520 @default.
• W2025794018 cites W2042899791 @default.
• W2025794018 cites W2043327592 @default.
• W2025794018 cites W2050189773 @default.
• W2025794018 cites W2050963402 @default.
• W2025794018 cites W2053078102 @default.
• W2025794018 cites W2056051109 @default.
• W2025794018 cites W2056781448 @default.
• W2025794018 cites W2058521792 @default.
• W2025794018 cites W2058629508 @default.
• W2025794018 cites W2058703481 @default.
• W2025794018 cites W2059257376 @default.
• W2025794018 cites W2062490212 @default.
• W2025794018 cites W2063162095 @default.
• W2025794018 cites W2064068872 @default.
• W2025794018 cites W2064555447 @default.
• W2025794018 cites W2066537800 @default.
• W2025794018 cites W2067373167 @default.
• W2025794018 cites W2067825493 @default.
• W2025794018 cites W2071187844 @default.
• W2025794018 cites W2071500761 @default.
• W2025794018 cites W2080190767 @default.
• W2025794018 cites W2082908877 @default.
• W2025794018 cites W2084402823 @default.
• W2025794018 cites W2086512162 @default.
• W2025794018 cites W2086957099 @default.
• W2025794018 cites W2089391612 @default.
• W2025794018 cites W2093905203 @default.
• W2025794018 cites W2095372317 @default.
• W2025794018 cites W2096592516 @default.
• W2025794018 cites W2125121216 @default.
• W2025794018 cites W2170153285 @default.
• W2025794018 cites W2334484395 @default.
• W2025794018 cites W2345354405 @default.
• W2025794018 cites W2569525354 @default.
• W2025794018 cites W271241064 @default.
• W2025794018 cites W291969710 @default.
• W2025794018 cites W2951669504 @default.
• W2025794018 cites W2952971329 @default.
• W2025794018 cites W2079923486 @default.
• W2025794018 doi "https://doi.org/10.1039/b103362j" @default.
• W2025794018 hasPublicationYear "2001" @default.
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