Rhodium and iridium complexes of 2-(bis(diphenylphosphino)methyl)pyridine (PNP). X-ray crystal and molecular structures of [Rh2(CO)2(PNP)2](PF6) 2·C3H6O and [Ir2(μ-CO)(CO)2(PNP)2](BF4) 2 and some chemistry of these and related complexes

Michael P. Anderson, C. C. Tso, Bruce M. Mattson, Louis H. Pignolet

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Abstract

Binuclear diphosphine-bridged complexes with the tridentate ligand 2-(bis(diphenylphosphino)methyl)pyridine, (Ph2P)2CHC5NH4 = PNP, have been prepared for rhodium and iridium. Two of the complexes, [Rh2(CO)2(PNP)2](P-F6) 2·C3H6O (1) and [Ir2(μ-CO)(CO)2(PNP)2](BF4) 2 (2), have been characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the orthorhombic space group Pbcn with Z = 4, a = 19.658 (7) Å, b = 18.528 (7) Å, c = 17.993 (6) Å, V = 6554 (7) Å3, and d = 1.553 g/cm3 while 2 crystallizes in the triclinic space group P1 with Z = 4, a = 16.387 (4) Å, b = 16.710 (6) Å, c = 24.710 (6) Å, α = 76.03 (2)°, β = 84.16 (2)°, γ = 75.37 (2)°, V = 6347 (4) Å3, and d = 1.638 g/cm3. Both complexes are of the diphosphine-bridged binuclear type with trans phosphorus atoms and with both pyridyl nitrogen atoms bonded to the metal atoms, giving five-membered PN chelate rings. The pyridyl nitrogen atoms are bonded to the metals on the same side of the binuclear complex. Complex 1 is of the face-to-face variety with a Rh⋯Rh separation of 3.054 (1) Å while 2 has a bridging CO ligand and approximate trigonal-bipyramidal geometry around each iridium atom. The Ir-Ir separation in 2 is 2.815 (1) Å and is consistent with the presence of an Ir-Ir bond. Complex 2 easily loses one CO ligand in solution, affording the iridium analogue of 1. Reactions of these complexes with nucleophiles such as halide and sulfide ions are described. Thus, 1 reacts with Cl- in acetone solution, giving the four-coordinate PN-bonded monomeric compound [Rh(Cl)(CO)(PNP)], which has a dangling phosphorus atom, whereas the analogous reaction with 2 gives the binuclear complex [Ir2(Cl)(CO)2(PNP)2]+, which has one bonded and one free pyridyl nitrogen atom. The reaction of 1 with S2- gives the binuclear sulfide-bridged A-frame complex [Rh2(μ-S)(CO)2(PNP)2], which has both pyridyl nitrogen atoms dangling. All of these complexes have been characterized by IR and 31P NMR spectroscopy, and their syntheses and properties are described.

Original languageEnglish
Pages (from-to)3267-3275
Number of pages9
JournalInorganic Chemistry
Volume22
Issue number22
StatePublished - 1983
Externally publishedYes

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Iridium
Rhodium
Carbon Monoxide
iridium
rhodium
Molecular structure
pyridines
molecular structure
Crystal structure
chemistry
X rays
Atoms
crystal structure
nitrogen atoms
x rays
Nitrogen
Sulfides
ligands
Ligands
atoms

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

@article{b9775f4103df4af88e4c57dee031bf75,
title = "Rhodium and iridium complexes of 2-(bis(diphenylphosphino)methyl)pyridine (PNP). X-ray crystal and molecular structures of [Rh2(CO)2(PNP)2](PF6) 2·C3H6O and [Ir2(μ-CO)(CO)2(PNP)2](BF4) 2 and some chemistry of these and related complexes",
abstract = "Binuclear diphosphine-bridged complexes with the tridentate ligand 2-(bis(diphenylphosphino)methyl)pyridine, (Ph2P)2CHC5NH4 = PNP, have been prepared for rhodium and iridium. Two of the complexes, [Rh2(CO)2(PNP)2](P-F6) 2·C3H6O (1) and [Ir2(μ-CO)(CO)2(PNP)2](BF4) 2 (2), have been characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the orthorhombic space group Pbcn with Z = 4, a = 19.658 (7) {\AA}, b = 18.528 (7) {\AA}, c = 17.993 (6) {\AA}, V = 6554 (7) {\AA}3, and d = 1.553 g/cm3 while 2 crystallizes in the triclinic space group P1 with Z = 4, a = 16.387 (4) {\AA}, b = 16.710 (6) {\AA}, c = 24.710 (6) {\AA}, α = 76.03 (2)°, β = 84.16 (2)°, γ = 75.37 (2)°, V = 6347 (4) {\AA}3, and d = 1.638 g/cm3. Both complexes are of the diphosphine-bridged binuclear type with trans phosphorus atoms and with both pyridyl nitrogen atoms bonded to the metal atoms, giving five-membered PN chelate rings. The pyridyl nitrogen atoms are bonded to the metals on the same side of the binuclear complex. Complex 1 is of the face-to-face variety with a Rh⋯Rh separation of 3.054 (1) {\AA} while 2 has a bridging CO ligand and approximate trigonal-bipyramidal geometry around each iridium atom. The Ir-Ir separation in 2 is 2.815 (1) {\AA} and is consistent with the presence of an Ir-Ir bond. Complex 2 easily loses one CO ligand in solution, affording the iridium analogue of 1. Reactions of these complexes with nucleophiles such as halide and sulfide ions are described. Thus, 1 reacts with Cl- in acetone solution, giving the four-coordinate PN-bonded monomeric compound [Rh(Cl)(CO)(PNP)], which has a dangling phosphorus atom, whereas the analogous reaction with 2 gives the binuclear complex [Ir2(Cl)(CO)2(PNP)2]+, which has one bonded and one free pyridyl nitrogen atom. The reaction of 1 with S2- gives the binuclear sulfide-bridged A-frame complex [Rh2(μ-S)(CO)2(PNP)2], which has both pyridyl nitrogen atoms dangling. All of these complexes have been characterized by IR and 31P NMR spectroscopy, and their syntheses and properties are described.",
author = "Anderson, {Michael P.} and Tso, {C. C.} and Mattson, {Bruce M.} and Pignolet, {Louis H.}",
year = "1983",
language = "English",
volume = "22",
pages = "3267--3275",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "22",

}

TY - JOUR

T1 - Rhodium and iridium complexes of 2-(bis(diphenylphosphino)methyl)pyridine (PNP). X-ray crystal and molecular structures of [Rh2(CO)2(PNP)2](PF6) 2·C3H6O and [Ir2(μ-CO)(CO)2(PNP)2](BF4) 2 and some chemistry of these and related complexes

AU - Anderson, Michael P.

AU - Tso, C. C.

AU - Mattson, Bruce M.

AU - Pignolet, Louis H.

PY - 1983

Y1 - 1983

N2 - Binuclear diphosphine-bridged complexes with the tridentate ligand 2-(bis(diphenylphosphino)methyl)pyridine, (Ph2P)2CHC5NH4 = PNP, have been prepared for rhodium and iridium. Two of the complexes, [Rh2(CO)2(PNP)2](P-F6) 2·C3H6O (1) and [Ir2(μ-CO)(CO)2(PNP)2](BF4) 2 (2), have been characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the orthorhombic space group Pbcn with Z = 4, a = 19.658 (7) Å, b = 18.528 (7) Å, c = 17.993 (6) Å, V = 6554 (7) Å3, and d = 1.553 g/cm3 while 2 crystallizes in the triclinic space group P1 with Z = 4, a = 16.387 (4) Å, b = 16.710 (6) Å, c = 24.710 (6) Å, α = 76.03 (2)°, β = 84.16 (2)°, γ = 75.37 (2)°, V = 6347 (4) Å3, and d = 1.638 g/cm3. Both complexes are of the diphosphine-bridged binuclear type with trans phosphorus atoms and with both pyridyl nitrogen atoms bonded to the metal atoms, giving five-membered PN chelate rings. The pyridyl nitrogen atoms are bonded to the metals on the same side of the binuclear complex. Complex 1 is of the face-to-face variety with a Rh⋯Rh separation of 3.054 (1) Å while 2 has a bridging CO ligand and approximate trigonal-bipyramidal geometry around each iridium atom. The Ir-Ir separation in 2 is 2.815 (1) Å and is consistent with the presence of an Ir-Ir bond. Complex 2 easily loses one CO ligand in solution, affording the iridium analogue of 1. Reactions of these complexes with nucleophiles such as halide and sulfide ions are described. Thus, 1 reacts with Cl- in acetone solution, giving the four-coordinate PN-bonded monomeric compound [Rh(Cl)(CO)(PNP)], which has a dangling phosphorus atom, whereas the analogous reaction with 2 gives the binuclear complex [Ir2(Cl)(CO)2(PNP)2]+, which has one bonded and one free pyridyl nitrogen atom. The reaction of 1 with S2- gives the binuclear sulfide-bridged A-frame complex [Rh2(μ-S)(CO)2(PNP)2], which has both pyridyl nitrogen atoms dangling. All of these complexes have been characterized by IR and 31P NMR spectroscopy, and their syntheses and properties are described.

AB - Binuclear diphosphine-bridged complexes with the tridentate ligand 2-(bis(diphenylphosphino)methyl)pyridine, (Ph2P)2CHC5NH4 = PNP, have been prepared for rhodium and iridium. Two of the complexes, [Rh2(CO)2(PNP)2](P-F6) 2·C3H6O (1) and [Ir2(μ-CO)(CO)2(PNP)2](BF4) 2 (2), have been characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the orthorhombic space group Pbcn with Z = 4, a = 19.658 (7) Å, b = 18.528 (7) Å, c = 17.993 (6) Å, V = 6554 (7) Å3, and d = 1.553 g/cm3 while 2 crystallizes in the triclinic space group P1 with Z = 4, a = 16.387 (4) Å, b = 16.710 (6) Å, c = 24.710 (6) Å, α = 76.03 (2)°, β = 84.16 (2)°, γ = 75.37 (2)°, V = 6347 (4) Å3, and d = 1.638 g/cm3. Both complexes are of the diphosphine-bridged binuclear type with trans phosphorus atoms and with both pyridyl nitrogen atoms bonded to the metal atoms, giving five-membered PN chelate rings. The pyridyl nitrogen atoms are bonded to the metals on the same side of the binuclear complex. Complex 1 is of the face-to-face variety with a Rh⋯Rh separation of 3.054 (1) Å while 2 has a bridging CO ligand and approximate trigonal-bipyramidal geometry around each iridium atom. The Ir-Ir separation in 2 is 2.815 (1) Å and is consistent with the presence of an Ir-Ir bond. Complex 2 easily loses one CO ligand in solution, affording the iridium analogue of 1. Reactions of these complexes with nucleophiles such as halide and sulfide ions are described. Thus, 1 reacts with Cl- in acetone solution, giving the four-coordinate PN-bonded monomeric compound [Rh(Cl)(CO)(PNP)], which has a dangling phosphorus atom, whereas the analogous reaction with 2 gives the binuclear complex [Ir2(Cl)(CO)2(PNP)2]+, which has one bonded and one free pyridyl nitrogen atom. The reaction of 1 with S2- gives the binuclear sulfide-bridged A-frame complex [Rh2(μ-S)(CO)2(PNP)2], which has both pyridyl nitrogen atoms dangling. All of these complexes have been characterized by IR and 31P NMR spectroscopy, and their syntheses and properties are described.

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