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) 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 language | English |
|---|---|
| Pages (from-to) | 3014-3018 |
| Number of pages | 5 |
| Journal | Inorganica Chimica Acta |
| Volume | 357 |
| Issue number | 10 |
| DOIs | |
| Publication status | Published - Jul 20 2004 |
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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 journal › Article
}
TY - JOUR
T1 - A hexanuclear iridium complex with a novel binding mode of a PCP-pincer ligand
AU - Zhang, Xiawei
AU - Emge, Thomas J.
AU - Goldman, Alan S
PY - 2004/7/20
Y1 - 2004/7/20
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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U2 - 10.1016/j.ica.2004.02.026
DO - 10.1016/j.ica.2004.02.026
M3 - Article
VL - 357
SP - 3014
EP - 3018
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
SN - 0020-1693
IS - 10
ER -