Addition of palladium and platinum tri-tert-butylphosphine groups to Re-Sn and Re-Ge Bonds

Richard D. Adams, Burjor Captain, Rolfe H. Herber, Mikael Johansson, Israel Nowik, Jack L. Smith, Mark D. Smith

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

The reaction of Re2(CO)8[μ-η2-C(H)= C(H)Bun](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)Bun](μ-H) with Ph3GeH. Compound 11 has a structure similar to that of 10. The reaction of 10 with Pd(PBut3)2 at 25°C yielded the bis-Pd(PBut3) adduct, Re2(CO) 8(μ-SnPh2)2[Pd(PBut 3)]2 (12); it has two Pd(PBut3) groups bridging two of the four Re-Sn bonds in 10. Fenske-Hall molecular orbital calculations show that the Pd(PBut3) groups form three-center two-electron bonds with the neighboring rhenium and tin atoms. The mono- and bis-Pt(PBut3) adducts, Re2(CO) 8(μ-SnPh2)2[Pt(PBut3)] (13) and Re2(CO)8(μ-SnPh2) 2[Pt(PBut3)]2 (14), were formed when 10 was treated with Pt(PBut3)2. A mono adduct of 11, Re2(CO)8(μ-GePh2) 2[Pt(PBut3)] (15), was obtained similarly from the reaction of 11 with Pt(PBut3)2.

Original languageEnglish
Pages (from-to)6346-6358
Number of pages13
JournalInorganic Chemistry
Volume44
Issue number18
DOIs
StatePublished - Sep 5 2005
Externally publishedYes

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Palladium
Platinum
palladium
Orbital calculations
platinum
Molecular orbitals
adducts
Isomers
Germanium compounds
Rhenium
molecular orbitals
germanium compounds
isomers
Tin
quadrupoles
Temperature
shift
rhenium
Ligands
temperature

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Adams, R. D., Captain, B., Herber, R. H., Johansson, M., Nowik, I., Smith, J. L., & Smith, M. D. (2005). Addition of palladium and platinum tri-tert-butylphosphine groups to Re-Sn and Re-Ge Bonds. Inorganic Chemistry, 44(18), 6346-6358. https://doi.org/10.1021/ic051077x

Addition of palladium and platinum tri-tert-butylphosphine groups to Re-Sn and Re-Ge Bonds. / Adams, Richard D.; Captain, Burjor; Herber, Rolfe H.; Johansson, Mikael; Nowik, Israel; Smith, Jack L.; Smith, Mark D.

In: Inorganic Chemistry, Vol. 44, No. 18, 05.09.2005, p. 6346-6358.

Research output: Contribution to journalArticle

Adams, RD, Captain, B, Herber, RH, Johansson, M, Nowik, I, Smith, JL & Smith, MD 2005, 'Addition of palladium and platinum tri-tert-butylphosphine groups to Re-Sn and Re-Ge Bonds', Inorganic Chemistry, vol. 44, no. 18, pp. 6346-6358. https://doi.org/10.1021/ic051077x
Adams, Richard D. ; Captain, Burjor ; Herber, Rolfe H. ; Johansson, Mikael ; Nowik, Israel ; Smith, Jack L. ; Smith, Mark D. / Addition of palladium and platinum tri-tert-butylphosphine groups to Re-Sn and Re-Ge Bonds. In: Inorganic Chemistry. 2005 ; Vol. 44, No. 18. pp. 6346-6358.
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abstract = "The reaction of Re2(CO)8[μ-η2-C(H)= C(H)Bun](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 M{\"o}ssbauer 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)Bun](μ-H) with Ph3GeH. Compound 11 has a structure similar to that of 10. The reaction of 10 with Pd(PBut3)2 at 25°C yielded the bis-Pd(PBut3) adduct, Re2(CO) 8(μ-SnPh2)2[Pd(PBut 3)]2 (12); it has two Pd(PBut3) groups bridging two of the four Re-Sn bonds in 10. Fenske-Hall molecular orbital calculations show that the Pd(PBut3) groups form three-center two-electron bonds with the neighboring rhenium and tin atoms. The mono- and bis-Pt(PBut3) adducts, Re2(CO) 8(μ-SnPh2)2[Pt(PBut3)] (13) and Re2(CO)8(μ-SnPh2) 2[Pt(PBut3)]2 (14), were formed when 10 was treated with Pt(PBut3)2. A mono adduct of 11, Re2(CO)8(μ-GePh2) 2[Pt(PBut3)] (15), was obtained similarly from the reaction of 11 with Pt(PBut3)2.",
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AU - Adams, Richard D.

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N2 - The reaction of Re2(CO)8[μ-η2-C(H)= C(H)Bun](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)Bun](μ-H) with Ph3GeH. Compound 11 has a structure similar to that of 10. The reaction of 10 with Pd(PBut3)2 at 25°C yielded the bis-Pd(PBut3) adduct, Re2(CO) 8(μ-SnPh2)2[Pd(PBut 3)]2 (12); it has two Pd(PBut3) groups bridging two of the four Re-Sn bonds in 10. Fenske-Hall molecular orbital calculations show that the Pd(PBut3) groups form three-center two-electron bonds with the neighboring rhenium and tin atoms. The mono- and bis-Pt(PBut3) adducts, Re2(CO) 8(μ-SnPh2)2[Pt(PBut3)] (13) and Re2(CO)8(μ-SnPh2) 2[Pt(PBut3)]2 (14), were formed when 10 was treated with Pt(PBut3)2. A mono adduct of 11, Re2(CO)8(μ-GePh2) 2[Pt(PBut3)] (15), was obtained similarly from the reaction of 11 with Pt(PBut3)2.

AB - The reaction of Re2(CO)8[μ-η2-C(H)= C(H)Bun](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)Bun](μ-H) with Ph3GeH. Compound 11 has a structure similar to that of 10. The reaction of 10 with Pd(PBut3)2 at 25°C yielded the bis-Pd(PBut3) adduct, Re2(CO) 8(μ-SnPh2)2[Pd(PBut 3)]2 (12); it has two Pd(PBut3) groups bridging two of the four Re-Sn bonds in 10. Fenske-Hall molecular orbital calculations show that the Pd(PBut3) groups form three-center two-electron bonds with the neighboring rhenium and tin atoms. The mono- and bis-Pt(PBut3) adducts, Re2(CO) 8(μ-SnPh2)2[Pt(PBut3)] (13) and Re2(CO)8(μ-SnPh2) 2[Pt(PBut3)]2 (14), were formed when 10 was treated with Pt(PBut3)2. A mono adduct of 11, Re2(CO)8(μ-GePh2) 2[Pt(PBut3)] (15), was obtained similarly from the reaction of 11 with Pt(PBut3)2.

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