High-nuclearity iridium carbonyl clusters containing phenylgermyl ligands: Synthesis, structures, and reactivity

Richard D. Adams, Burjor Captain, Jack L. Smith

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

The reaction of Ir4(CO)12 with Ph3GeH at 97°C has yielded the new tetrairidium cluster complexes Ir 4(CO)7-(GePh3)(μ-GePh2) 233-GePh(C6H 4)](μ-H)2 (10) and Ir4(CO) 8(GePh3)2(μ-GePh2)4 (11). The structure of 10 consists of a tetrahedral Ir4 cluster with seven terminal CO groups, two bridging GePh2 ligands, an ortho-metallated bridging μ33-GePh(C 6H4) group, a terminal GePh3 ligand, and two bridging hydrido ligands. Compound 11 consists of a planar butterfly arrangement of four iridium atoms with four bridging GePh2 and two terminal GePh3 ligands. The same reaction at 125°C yielded the two new triiridium clusters Ir3(CO)5(GePh3)(μ- GePh2)33-GePh)(μ-H) (12) and Ir 3(CO)6(GePh3)3(μ-GePh 2)3 (13). Compound 12 contains a triangular Ir3 cluster with three bridging GePh2, one triply bridging GePh, and one terminal GePh3 ligand. The compound also contains a hydrido ligand that bridges one of the Ir-Ge bonds. Compound 13 contains a triangular Ir 3 cluster with three bridging GePh2 and three terminal GePh3 ligands. At 151°C, an additional complex, Ir 4H4(CO)4(μ-GePh2) 44-GePh)2 (14), was isolated. Compound 14 consists of an Ir4 square with four bridging GePh2, two quadruply bridging GePh groups, and four terminal hydrido ligands. Compound 12 reacts with CO at 125°C to give the compound Ir3(CO) 6(μ-GePh2)33-GePh) (15). Compound 15 is formed via the loss of the hydrido ligand and the terminal GePh3 ligand and the addition of one carbonyl ligand to 12. All compounds were fully characterized by IR, NMR, single-crystal X-ray diffraction analysis, and elemental analysis.

Original languageEnglish
Pages (from-to)1413-1420
Number of pages8
JournalInorganic Chemistry
Volume44
Issue number5
DOIs
StatePublished - Mar 7 2005
Externally publishedYes

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Iridium
iridium
reactivity
Ligands
ligands
synthesis
Carbon Monoxide
X ray diffraction analysis
Nuclear magnetic resonance
Single crystals

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

High-nuclearity iridium carbonyl clusters containing phenylgermyl ligands : Synthesis, structures, and reactivity. / Adams, Richard D.; Captain, Burjor; Smith, Jack L.

In: Inorganic Chemistry, Vol. 44, No. 5, 07.03.2005, p. 1413-1420.

Research output: Contribution to journalArticle

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title = "High-nuclearity iridium carbonyl clusters containing phenylgermyl ligands: Synthesis, structures, and reactivity",
abstract = "The reaction of Ir4(CO)12 with Ph3GeH at 97°C has yielded the new tetrairidium cluster complexes Ir 4(CO)7-(GePh3)(μ-GePh2) 2[μ3-η3-GePh(C6H 4)](μ-H)2 (10) and Ir4(CO) 8(GePh3)2(μ-GePh2)4 (11). The structure of 10 consists of a tetrahedral Ir4 cluster with seven terminal CO groups, two bridging GePh2 ligands, an ortho-metallated bridging μ3-η3-GePh(C 6H4) group, a terminal GePh3 ligand, and two bridging hydrido ligands. Compound 11 consists of a planar butterfly arrangement of four iridium atoms with four bridging GePh2 and two terminal GePh3 ligands. The same reaction at 125°C yielded the two new triiridium clusters Ir3(CO)5(GePh3)(μ- GePh2)3(μ3-GePh)(μ-H) (12) and Ir 3(CO)6(GePh3)3(μ-GePh 2)3 (13). Compound 12 contains a triangular Ir3 cluster with three bridging GePh2, one triply bridging GePh, and one terminal GePh3 ligand. The compound also contains a hydrido ligand that bridges one of the Ir-Ge bonds. Compound 13 contains a triangular Ir 3 cluster with three bridging GePh2 and three terminal GePh3 ligands. At 151°C, an additional complex, Ir 4H4(CO)4(μ-GePh2) 4(μ4-GePh)2 (14), was isolated. Compound 14 consists of an Ir4 square with four bridging GePh2, two quadruply bridging GePh groups, and four terminal hydrido ligands. Compound 12 reacts with CO at 125°C to give the compound Ir3(CO) 6(μ-GePh2)3(μ3-GePh) (15). Compound 15 is formed via the loss of the hydrido ligand and the terminal GePh3 ligand and the addition of one carbonyl ligand to 12. All compounds were fully characterized by IR, NMR, single-crystal X-ray diffraction analysis, and elemental analysis.",
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N2 - The reaction of Ir4(CO)12 with Ph3GeH at 97°C has yielded the new tetrairidium cluster complexes Ir 4(CO)7-(GePh3)(μ-GePh2) 2[μ3-η3-GePh(C6H 4)](μ-H)2 (10) and Ir4(CO) 8(GePh3)2(μ-GePh2)4 (11). The structure of 10 consists of a tetrahedral Ir4 cluster with seven terminal CO groups, two bridging GePh2 ligands, an ortho-metallated bridging μ3-η3-GePh(C 6H4) group, a terminal GePh3 ligand, and two bridging hydrido ligands. Compound 11 consists of a planar butterfly arrangement of four iridium atoms with four bridging GePh2 and two terminal GePh3 ligands. The same reaction at 125°C yielded the two new triiridium clusters Ir3(CO)5(GePh3)(μ- GePh2)3(μ3-GePh)(μ-H) (12) and Ir 3(CO)6(GePh3)3(μ-GePh 2)3 (13). Compound 12 contains a triangular Ir3 cluster with three bridging GePh2, one triply bridging GePh, and one terminal GePh3 ligand. The compound also contains a hydrido ligand that bridges one of the Ir-Ge bonds. Compound 13 contains a triangular Ir 3 cluster with three bridging GePh2 and three terminal GePh3 ligands. At 151°C, an additional complex, Ir 4H4(CO)4(μ-GePh2) 4(μ4-GePh)2 (14), was isolated. Compound 14 consists of an Ir4 square with four bridging GePh2, two quadruply bridging GePh groups, and four terminal hydrido ligands. Compound 12 reacts with CO at 125°C to give the compound Ir3(CO) 6(μ-GePh2)3(μ3-GePh) (15). Compound 15 is formed via the loss of the hydrido ligand and the terminal GePh3 ligand and the addition of one carbonyl ligand to 12. All compounds were fully characterized by IR, NMR, single-crystal X-ray diffraction analysis, and elemental analysis.

AB - The reaction of Ir4(CO)12 with Ph3GeH at 97°C has yielded the new tetrairidium cluster complexes Ir 4(CO)7-(GePh3)(μ-GePh2) 2[μ3-η3-GePh(C6H 4)](μ-H)2 (10) and Ir4(CO) 8(GePh3)2(μ-GePh2)4 (11). The structure of 10 consists of a tetrahedral Ir4 cluster with seven terminal CO groups, two bridging GePh2 ligands, an ortho-metallated bridging μ3-η3-GePh(C 6H4) group, a terminal GePh3 ligand, and two bridging hydrido ligands. Compound 11 consists of a planar butterfly arrangement of four iridium atoms with four bridging GePh2 and two terminal GePh3 ligands. The same reaction at 125°C yielded the two new triiridium clusters Ir3(CO)5(GePh3)(μ- GePh2)3(μ3-GePh)(μ-H) (12) and Ir 3(CO)6(GePh3)3(μ-GePh 2)3 (13). Compound 12 contains a triangular Ir3 cluster with three bridging GePh2, one triply bridging GePh, and one terminal GePh3 ligand. The compound also contains a hydrido ligand that bridges one of the Ir-Ge bonds. Compound 13 contains a triangular Ir 3 cluster with three bridging GePh2 and three terminal GePh3 ligands. At 151°C, an additional complex, Ir 4H4(CO)4(μ-GePh2) 4(μ4-GePh)2 (14), was isolated. Compound 14 consists of an Ir4 square with four bridging GePh2, two quadruply bridging GePh groups, and four terminal hydrido ligands. Compound 12 reacts with CO at 125°C to give the compound Ir3(CO) 6(μ-GePh2)3(μ3-GePh) (15). Compound 15 is formed via the loss of the hydrido ligand and the terminal GePh3 ligand and the addition of one carbonyl ligand to 12. All compounds were fully characterized by IR, NMR, single-crystal X-ray diffraction analysis, and elemental analysis.

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