Addition of Palladium and Platinum Tri-tert-Butylphosphine Groups to Re−Sn and Re−Ge Bonds
The reaction of Re2(CO)8[μ-η2-C(H)C(H)Bu n ](μ-H) with Ph3SnH at 68 °C yielded the new compound Re2(CO)8(μ-SnPh2)2 (10) which contains two SnPh2 ligands bridging two Re(CO)4 groups, joined by an unusually long Re−Re bond. Fenske−Hall molecular orbital calculations indicate that the bonding in the R...
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Published in | Inorganic chemistry Vol. 44; no. 18; pp. 6346 - 6358 |
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Main Authors | , , , , , , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
05.09.2005
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Online Access | Get full text |
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Summary: | The reaction of Re2(CO)8[μ-η2-C(H)C(H)Bu n ](μ-H) with Ph3SnH at 68 °C yielded the new compound Re2(CO)8(μ-SnPh2)2 (10) which contains two SnPh2 ligands bridging two Re(CO)4 groups, joined by an unusually long Re−Re bond. Fenske−Hall molecular orbital calculations indicate that the bonding in the Re2Sn2 cluster is dominated by strong Re−Sn interactions and that the Re−Re interactions are weak. The 119Sn Mössbauer spectrum of 10 exhibits a doublet with an isomer shift (IS) of 1.674(12) mm s-1 and a quadrupole splitting (QS) of 2.080(12) mm s-1 at 90 K,characteristic of Sn(IV) in a SnA2B2 environment. The IS is temperature dependent, −1.99(14) × 10-4 mm s-1 K-1; the QS is temperature independent. The temperature-dependent properties are consistent with the known Gol'danskii−Kariagin effect. The germanium compound Re2(CO)8(μ-GePh2)2 (11) was obtained from the reaction of Re2(CO)8[μ-η2-C(H)C(H)Bu n ](μ-H) with Ph3GeH. Compound 11 has a structure similar to that of 10. The reaction of 10 with Pd(PBu t 3)2 at 25 °C yielded the bis-Pd(PBu t 3) adduct, Re2(CO)8(μ-SnPh2)2[Pd(PBu t 3)]2 (12); it has two Pd(PBu t 3) groups bridging two of the four Re−Sn bonds in 10. Fenske−Hall molecular orbital calculations show that the Pd(PBu t 3) groups form three-center two-electron bonds with the neighboring rhenium and tin atoms. The mono- and bis-Pt(PBu t 3) adducts, Re2(CO)8(μ-SnPh2)2[Pt(PBu t 3)] (13) and Re2(CO)8(μ-SnPh2)2[Pt(PBu t 3)]2 (14), were formed when 10 was treated with Pt(PBu t 3)2. A mono adduct of 11, Re2(CO)8(μ-GePh2)2[Pt(PBu t 3)] (15), was obtained similarly from the reaction of 11 with Pt(PBu t 3)2. |
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Bibliography: | ark:/67375/TPS-PRT7BH31-B istex:470DC32AD33755FE877B5B33F74BAC86B0ACE63B ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0020-1669 1520-510X |
DOI: | 10.1021/ic051077x |