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• W2016237208 abstract "Abstract Twice as reactive : The coordination chemistry of phosphane‐functionalized Zr and Hf cycloheptatrienyl–cyclopentadienyl complexes gives rise to unusual secondary interactions associated with the presence of Lewis acidic 16‐electron sandwich moieties. These structures can develop weak dative bonds as exemplified by the noncovalent Pd→Zr interaction in the heterobimetallic {Zr 2 Pd} complex (see picture). magnified image Phosphane‐functionalized cycloheptatrienyl–cyclopentadienyl Group 4 metal complexes of the type [(η 7 ‐C 7 H 7 )M(η 5 ‐C 5 H 4 PR 2 )] (M=Ti ( 9 ); M=Zr ( 10 ); M=Hf ( 11 ); R=Ph ( a ); R= i Pr ( b )) have been prepared by the reduction of [(η 5 ‐C 5 H 4 PR 2 )TiCl 3 ] or [(η 5 ‐C 5 H 4 PR 2 ) 2 MCl 2 ] (M=Zr, Hf) with magnesium in the presence of cycloheptatriene (C 7 H 8 ). In the solid state, the Ti complex 9 a and the complex 11 b are monomeric, whereas 10 a , 10 b , and 11 a form dimers, in which the sandwich units are linked by long ZrP or HfP bonds. Density‐functional theory (DFT) calculations indicate that the metal–phosphane interaction is weak, and accordingly, both the Ti complex 9 b and the Zr complex 10 b act as monodentate phosphane ligands upon reaction with [{(cod)RhCl} 2 ] (cod=η 4 ‐1,5‐cyclooctadiene). The X‐ray crystal structures of [(cod)Rh( 9 b )Cl] ( 12 ) and [(cod)Rh( 10 b )Cl] ( 13 ) reveal that only the latter exhibits a secondary intramolecular Cl–metal interaction. The complex [( 10 b ) 2 Pd] ( 14 ) was obtained by reaction of [(η 5 ‐C 5 H 5 )Pd(η 3 ‐C 3 H 5 )] with two equivalents of 10 b . The solid‐state structure of 14 reveals a T‐shaped Pd 0 center with a long PdZr bond of 2.9709(3) Å, which can be interpreted as a weak noncovalent Pd 0 →Zr +IV bond, as indicated by the calculated relaxed force constant of 5.68 N m −1 ." @default.
• W2016237208 created "2016-06-24" @default.
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• W2016237208 date "2009-02-06" @default.
• W2016237208 modified "2023-10-14" @default.
• W2016237208 title "Secondary Interactions in Phosphane‐Functionalized Group 4 Cycloheptatrienyl–Cyclopentadienyl Sandwich Complexes" @default.
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• W2016237208 doi "https://doi.org/10.1002/chem.200802518" @default.
• W2016237208 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/19145604" @default.
• W2016237208 hasPublicationYear "2009" @default.

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