A hexanuclear iridium complex with a novel binding mode of a PCP-pincer ligand

Xiawei Zhang, Thomas J. Emge, Alan S Goldman

Research output: Contribution to journalArticle

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Abstract

The hexanuclear iridium complex [η4-(COD)Ir] 26-[κ4-C6H 2(CH2PtBu2)2]Ir 2H2Cl3} (1) has been prepared by the reaction of [Ir(COD)Cl]2 with the "PCP" ligand precursor, 1,3-C 6H4(CH2PtBu2) 2 (PCP-H). Characterization by X-ray diffraction reveals that complex 1 has an unusual structure in which metalation (C-H addition) of the ligand has occurred at the 4- and 6-positions of the PCP aryl ring. This is in contrast to the widespread reactivity of this ligand precursor in which a single metalation typically occurs at the 2-position, thereby allowing coordination of both phosphino groups to a single metal center to give the κ3- meridional pincer coordination. The complex can be viewed as being composed of a dimer of two bis-metalated (Ir(III)) PCP units, held together by two bridges of three chlorides each; the aryl ring of each of the PCP ligands of this hypothetical tetra-iridium dianion is then bound to a cationic [Ir(I)(COD)] + unit. The structure discussed here crystallizes as the tetra(acetone) solvate in the monoclinic space group P21/n with lattice parameters a=14.4154(11) Å, b=15.4435(12) Å, c=19.5181(15) Å, b=99.996(1)°and V=4279.31(6) Å3. Convergence to conventional R values of R(F)=0.041 and Rw(F)=0.092 was obtained for 445 variable parameters and 8085 reflections with F>4σ(F). Complex 1 also crystallizes as the octabenzene solvate in the orthorhombic space group Pbca, with lattice parameters a=16.4247(14) Å, b=24.1695(21) Å, c=28.0460(24) Å and V=11134(1) Å3. Convergence of the orthorhombic phase to R(F)=0.038 and Rw(F)=0.084 was obtained for 595 variable parameters and 12885 reflections with F>4σ(F).

Original languageEnglish
Pages (from-to)3014-3018
Number of pages5
JournalInorganica Chimica Acta
Volume357
Issue number10
DOIs
Publication statusPublished - Jul 20 2004

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Iridium
iridium
crack opening displacement
Ligands
ligands
Lattice constants
lattice parameters
rings
Acetone
X-Ray Diffraction
Dimers
acetone
Chlorides
reactivity
Metals
chlorides
dimers
X ray diffraction
diffraction
metals

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

A hexanuclear iridium complex with a novel binding mode of a PCP-pincer ligand. / Zhang, Xiawei; Emge, Thomas J.; Goldman, Alan S.

In: Inorganica Chimica Acta, Vol. 357, No. 10, 20.07.2004, p. 3014-3018.

Research output: Contribution to journalArticle

Zhang, Xiawei ; Emge, Thomas J. ; Goldman, Alan S. / A hexanuclear iridium complex with a novel binding mode of a PCP-pincer ligand. In: Inorganica Chimica Acta. 2004 ; Vol. 357, No. 10. pp. 3014-3018.
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title = "A hexanuclear iridium complex with a novel binding mode of a PCP-pincer ligand",
abstract = "The hexanuclear iridium complex [η4-(COD)Ir] 2{η6-[κ4-C6H 2(CH2PtBu2)2]Ir 2H2Cl3} (1) has been prepared by the reaction of [Ir(COD)Cl]2 with the {"}PCP{"} ligand precursor, 1,3-C 6H4(CH2PtBu2) 2 (PCP-H). Characterization by X-ray diffraction reveals that complex 1 has an unusual structure in which metalation (C-H addition) of the ligand has occurred at the 4- and 6-positions of the PCP aryl ring. This is in contrast to the widespread reactivity of this ligand precursor in which a single metalation typically occurs at the 2-position, thereby allowing coordination of both phosphino groups to a single metal center to give the κ3- meridional pincer coordination. The complex can be viewed as being composed of a dimer of two bis-metalated (Ir(III)) PCP units, held together by two bridges of three chlorides each; the aryl ring of each of the PCP ligands of this hypothetical tetra-iridium dianion is then bound to a cationic [Ir(I)(COD)] + unit. The structure discussed here crystallizes as the tetra(acetone) solvate in the monoclinic space group P21/n with lattice parameters a=14.4154(11) {\AA}, b=15.4435(12) {\AA}, c=19.5181(15) {\AA}, b=99.996(1)°and V=4279.31(6) {\AA}3. Convergence to conventional R values of R(F)=0.041 and Rw(F)=0.092 was obtained for 445 variable parameters and 8085 reflections with F>4σ(F). Complex 1 also crystallizes as the octabenzene solvate in the orthorhombic space group Pbca, with lattice parameters a=16.4247(14) {\AA}, b=24.1695(21) {\AA}, c=28.0460(24) {\AA} and V=11134(1) {\AA}3. Convergence of the orthorhombic phase to R(F)=0.038 and Rw(F)=0.084 was obtained for 595 variable parameters and 12885 reflections with F>4σ(F).",
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N2 - The hexanuclear iridium complex [η4-(COD)Ir] 2{η6-[κ4-C6H 2(CH2PtBu2)2]Ir 2H2Cl3} (1) has been prepared by the reaction of [Ir(COD)Cl]2 with the "PCP" ligand precursor, 1,3-C 6H4(CH2PtBu2) 2 (PCP-H). Characterization by X-ray diffraction reveals that complex 1 has an unusual structure in which metalation (C-H addition) of the ligand has occurred at the 4- and 6-positions of the PCP aryl ring. This is in contrast to the widespread reactivity of this ligand precursor in which a single metalation typically occurs at the 2-position, thereby allowing coordination of both phosphino groups to a single metal center to give the κ3- meridional pincer coordination. The complex can be viewed as being composed of a dimer of two bis-metalated (Ir(III)) PCP units, held together by two bridges of three chlorides each; the aryl ring of each of the PCP ligands of this hypothetical tetra-iridium dianion is then bound to a cationic [Ir(I)(COD)] + unit. The structure discussed here crystallizes as the tetra(acetone) solvate in the monoclinic space group P21/n with lattice parameters a=14.4154(11) Å, b=15.4435(12) Å, c=19.5181(15) Å, b=99.996(1)°and V=4279.31(6) Å3. Convergence to conventional R values of R(F)=0.041 and Rw(F)=0.092 was obtained for 445 variable parameters and 8085 reflections with F>4σ(F). Complex 1 also crystallizes as the octabenzene solvate in the orthorhombic space group Pbca, with lattice parameters a=16.4247(14) Å, b=24.1695(21) Å, c=28.0460(24) Å and V=11134(1) Å3. Convergence of the orthorhombic phase to R(F)=0.038 and Rw(F)=0.084 was obtained for 595 variable parameters and 12885 reflections with F>4σ(F).

AB - The hexanuclear iridium complex [η4-(COD)Ir] 2{η6-[κ4-C6H 2(CH2PtBu2)2]Ir 2H2Cl3} (1) has been prepared by the reaction of [Ir(COD)Cl]2 with the "PCP" ligand precursor, 1,3-C 6H4(CH2PtBu2) 2 (PCP-H). Characterization by X-ray diffraction reveals that complex 1 has an unusual structure in which metalation (C-H addition) of the ligand has occurred at the 4- and 6-positions of the PCP aryl ring. This is in contrast to the widespread reactivity of this ligand precursor in which a single metalation typically occurs at the 2-position, thereby allowing coordination of both phosphino groups to a single metal center to give the κ3- meridional pincer coordination. The complex can be viewed as being composed of a dimer of two bis-metalated (Ir(III)) PCP units, held together by two bridges of three chlorides each; the aryl ring of each of the PCP ligands of this hypothetical tetra-iridium dianion is then bound to a cationic [Ir(I)(COD)] + unit. The structure discussed here crystallizes as the tetra(acetone) solvate in the monoclinic space group P21/n with lattice parameters a=14.4154(11) Å, b=15.4435(12) Å, c=19.5181(15) Å, b=99.996(1)°and V=4279.31(6) Å3. Convergence to conventional R values of R(F)=0.041 and Rw(F)=0.092 was obtained for 445 variable parameters and 8085 reflections with F>4σ(F). Complex 1 also crystallizes as the octabenzene solvate in the orthorhombic space group Pbca, with lattice parameters a=16.4247(14) Å, b=24.1695(21) Å, c=28.0460(24) Å and V=11134(1) Å3. Convergence of the orthorhombic phase to R(F)=0.038 and Rw(F)=0.084 was obtained for 595 variable parameters and 12885 reflections with F>4σ(F).

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