Rhodium and iridium complexes with the PN donor ligand (C6H5)2P(CH2)2C 5H4N. Crystal and molecular structures of Ir(PN)2(CO)Cl, Ir(PN)(CO)Cl, and [Rh(PN)2]PF6

Michael P. Anderson, Albert L. Casalnuovo, Brian J. Johnson, Bruce M. Mattson, Ann M. Mueting, Louis H. Pignolet

Research output: Contribution to journalArticle

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Abstract

Several new PN [1-(2-pyridyl)-2-(diphenylphosphino)ethane] complexes of rhodium and iridium have been synthesized. [Ir(PN)2]+ (1) was synthesized from [Ir(PN)(cod)]+ (cod = cyclooctadiene) and an excess of PN in acetone solution and characterized by IR, 1H NMR, and 31P NMR spectroscopy. 1 reacted with H2 in acetonitrile solution to form the cis-dihydride [Ir(PN)2(H)2]+ (2). Ir(PN)2(CO)Cl (3) and Ir(PN)(CO)Cl (4) were synthesized from the reaction of 2-methoxyethanol solutions of [Ir(CO)2Cl2]- with 2 and 1 equiv of PN, respectively. These four-coordinate square-planar complexes were characterized by IR and 31P NMR spectroscopy and by single-crystal X-ray analysis (3, monoclinic P21/a, a = 13.178 (2) Å, b = 13.579 (2) Å, c = 9.672 (2) Å, β = 93.84 (1)°, Z = 2, R = 0.025; 4-Et2O, triclinic P1, a = 11.079 (3) Å, b = 12.901 (3) Å, c = 8.377 (3) Å, α = 101.95 (3)°, β = 109.50 (3)°, γ = 73.01 (2)°, Z = 2, R = 0.025). In 3, both PN ligands are monodentate coordinated through the phosphorus atom. [Ir(PN)2(CO)]+ (5) was synthesized from 3 with KPF6 in acetone solution and characterized by IR and 31P NMR spectroscopy as a four-coordinate square-planar complex with one PN ligand bidentate and one monodentate bonded through the phosphorus atom. The reactivity of 5 with H2 and H+ was also examined. The reaction of PN with an acetone solution of [Rh(nbd)Cl]2 (nbd = norbornadiene) treated with AgPF6 produced a new chelated complex, [Rh(PN)2]PF6 (8(PF6)), which was characterized by IR and 31P NMR spectroscopy and by single-crystal X-ray diffraction (monoclinic P21/n, a = 10.714 (2) Å, 6 = 21.774 (2) Å, c = 15.915 (4) Å, β = 99.95 (2)°, Z = 4, R = 0.039), and was shown to have a distorted square-planar cis geometry. Complex 8 reacted with CO to form the carbonyl adduct, [Rh(PN)2(CO)]+ (9). The reaction of the tridentate ligand 2-[bis(diphenylphosphino)methyl]pyridine (PNP) with [Rh(CO)2Cl2]- under refluxing conditions of 2-methoxyethanol/toluene produced the 4-coordinate complex Rh(PN′)(CO)Cl (11). The ligand PN′ = 2-[(diphenylphosphino)methyl]pyridine resulted from P-C bond cleavage of PNP. The PN analogue of 11, Rh(PN)(CO)Cl (10), was also synthesized by reaction of [Rh(CO)2Cl2]-with PN in 2-methoxyethanol/toluene solution. Complexes 9-11 were characterized by IR and 31P NMR spectroscopy. The activities for the decarbonylation of benzaldehyde with use of 1(PF6) and 8(BF4) were found to be 9 and 10 turnovers/h, respectively, at 150°C in neat benzaldehyde, and their catalytic properties were studied. The results are discussed and compared to the catalytic activity and proposed mechanism of the decarbonylation reaction using [M(dppp)2]+ (M = Rh, Ir; dppp = 1,3-bis(diphenylphosphino)propane).

Original languageEnglish
Pages (from-to)1649-1658
Number of pages10
JournalInorganic Chemistry
Volume27
Issue number9
StatePublished - 1988
Externally publishedYes

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Iridium
Rhodium
Carbon Monoxide
iridium
rhodium
Molecular structure
molecular structure
Crystal structure
Ligands
nuclear magnetic resonance
ligands
crystal structure
acetone
Nuclear magnetic resonance spectroscopy
pyridines
spectroscopy
Acetone
phosphorus
toluene
Toluene

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

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Rhodium and iridium complexes with the PN donor ligand (C6H5)2P(CH2)2C 5H4N. Crystal and molecular structures of Ir(PN)2(CO)Cl, Ir(PN)(CO)Cl, and [Rh(PN)2]PF6 . / Anderson, Michael P.; Casalnuovo, Albert L.; Johnson, Brian J.; Mattson, Bruce M.; Mueting, Ann M.; Pignolet, Louis H.

In: Inorganic Chemistry, Vol. 27, No. 9, 1988, p. 1649-1658.

Research output: Contribution to journalArticle

Anderson, Michael P. ; Casalnuovo, Albert L. ; Johnson, Brian J. ; Mattson, Bruce M. ; Mueting, Ann M. ; Pignolet, Louis H. / Rhodium and iridium complexes with the PN donor ligand (C6H5)2P(CH2)2C 5H4N. Crystal and molecular structures of Ir(PN)2(CO)Cl, Ir(PN)(CO)Cl, and [Rh(PN)2]PF6 In: Inorganic Chemistry. 1988 ; Vol. 27, No. 9. pp. 1649-1658.
@article{576d8b4a6c534d8da3083aa57aee215b,
title = "Rhodium and iridium complexes with the PN donor ligand (C6H5)2P(CH2)2C 5H4N. Crystal and molecular structures of Ir(PN)2(CO)Cl, Ir(PN)(CO)Cl, and [Rh(PN)2]PF6",
abstract = "Several new PN [1-(2-pyridyl)-2-(diphenylphosphino)ethane] complexes of rhodium and iridium have been synthesized. [Ir(PN)2]+ (1) was synthesized from [Ir(PN)(cod)]+ (cod = cyclooctadiene) and an excess of PN in acetone solution and characterized by IR, 1H NMR, and 31P NMR spectroscopy. 1 reacted with H2 in acetonitrile solution to form the cis-dihydride [Ir(PN)2(H)2]+ (2). Ir(PN)2(CO)Cl (3) and Ir(PN)(CO)Cl (4) were synthesized from the reaction of 2-methoxyethanol solutions of [Ir(CO)2Cl2]- with 2 and 1 equiv of PN, respectively. These four-coordinate square-planar complexes were characterized by IR and 31P NMR spectroscopy and by single-crystal X-ray analysis (3, monoclinic P21/a, a = 13.178 (2) {\AA}, b = 13.579 (2) {\AA}, c = 9.672 (2) {\AA}, β = 93.84 (1)°, Z = 2, R = 0.025; 4-Et2O, triclinic P1, a = 11.079 (3) {\AA}, b = 12.901 (3) {\AA}, c = 8.377 (3) {\AA}, α = 101.95 (3)°, β = 109.50 (3)°, γ = 73.01 (2)°, Z = 2, R = 0.025). In 3, both PN ligands are monodentate coordinated through the phosphorus atom. [Ir(PN)2(CO)]+ (5) was synthesized from 3 with KPF6 in acetone solution and characterized by IR and 31P NMR spectroscopy as a four-coordinate square-planar complex with one PN ligand bidentate and one monodentate bonded through the phosphorus atom. The reactivity of 5 with H2 and H+ was also examined. The reaction of PN with an acetone solution of [Rh(nbd)Cl]2 (nbd = norbornadiene) treated with AgPF6 produced a new chelated complex, [Rh(PN)2]PF6 (8(PF6)), which was characterized by IR and 31P NMR spectroscopy and by single-crystal X-ray diffraction (monoclinic P21/n, a = 10.714 (2) {\AA}, 6 = 21.774 (2) {\AA}, c = 15.915 (4) {\AA}, β = 99.95 (2)°, Z = 4, R = 0.039), and was shown to have a distorted square-planar cis geometry. Complex 8 reacted with CO to form the carbonyl adduct, [Rh(PN)2(CO)]+ (9). The reaction of the tridentate ligand 2-[bis(diphenylphosphino)methyl]pyridine (PNP) with [Rh(CO)2Cl2]- under refluxing conditions of 2-methoxyethanol/toluene produced the 4-coordinate complex Rh(PN′)(CO)Cl (11). The ligand PN′ = 2-[(diphenylphosphino)methyl]pyridine resulted from P-C bond cleavage of PNP. The PN analogue of 11, Rh(PN)(CO)Cl (10), was also synthesized by reaction of [Rh(CO)2Cl2]-with PN in 2-methoxyethanol/toluene solution. Complexes 9-11 were characterized by IR and 31P NMR spectroscopy. The activities for the decarbonylation of benzaldehyde with use of 1(PF6) and 8(BF4) were found to be 9 and 10 turnovers/h, respectively, at 150°C in neat benzaldehyde, and their catalytic properties were studied. The results are discussed and compared to the catalytic activity and proposed mechanism of the decarbonylation reaction using [M(dppp)2]+ (M = Rh, Ir; dppp = 1,3-bis(diphenylphosphino)propane).",
author = "Anderson, {Michael P.} and Casalnuovo, {Albert L.} and Johnson, {Brian J.} and Mattson, {Bruce M.} and Mueting, {Ann M.} and Pignolet, {Louis H.}",
year = "1988",
language = "English",
volume = "27",
pages = "1649--1658",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "9",

}

TY - JOUR

T1 - Rhodium and iridium complexes with the PN donor ligand (C6H5)2P(CH2)2C 5H4N. Crystal and molecular structures of Ir(PN)2(CO)Cl, Ir(PN)(CO)Cl, and [Rh(PN)2]PF6

AU - Anderson, Michael P.

AU - Casalnuovo, Albert L.

AU - Johnson, Brian J.

AU - Mattson, Bruce M.

AU - Mueting, Ann M.

AU - Pignolet, Louis H.

PY - 1988

Y1 - 1988

N2 - Several new PN [1-(2-pyridyl)-2-(diphenylphosphino)ethane] complexes of rhodium and iridium have been synthesized. [Ir(PN)2]+ (1) was synthesized from [Ir(PN)(cod)]+ (cod = cyclooctadiene) and an excess of PN in acetone solution and characterized by IR, 1H NMR, and 31P NMR spectroscopy. 1 reacted with H2 in acetonitrile solution to form the cis-dihydride [Ir(PN)2(H)2]+ (2). Ir(PN)2(CO)Cl (3) and Ir(PN)(CO)Cl (4) were synthesized from the reaction of 2-methoxyethanol solutions of [Ir(CO)2Cl2]- with 2 and 1 equiv of PN, respectively. These four-coordinate square-planar complexes were characterized by IR and 31P NMR spectroscopy and by single-crystal X-ray analysis (3, monoclinic P21/a, a = 13.178 (2) Å, b = 13.579 (2) Å, c = 9.672 (2) Å, β = 93.84 (1)°, Z = 2, R = 0.025; 4-Et2O, triclinic P1, a = 11.079 (3) Å, b = 12.901 (3) Å, c = 8.377 (3) Å, α = 101.95 (3)°, β = 109.50 (3)°, γ = 73.01 (2)°, Z = 2, R = 0.025). In 3, both PN ligands are monodentate coordinated through the phosphorus atom. [Ir(PN)2(CO)]+ (5) was synthesized from 3 with KPF6 in acetone solution and characterized by IR and 31P NMR spectroscopy as a four-coordinate square-planar complex with one PN ligand bidentate and one monodentate bonded through the phosphorus atom. The reactivity of 5 with H2 and H+ was also examined. The reaction of PN with an acetone solution of [Rh(nbd)Cl]2 (nbd = norbornadiene) treated with AgPF6 produced a new chelated complex, [Rh(PN)2]PF6 (8(PF6)), which was characterized by IR and 31P NMR spectroscopy and by single-crystal X-ray diffraction (monoclinic P21/n, a = 10.714 (2) Å, 6 = 21.774 (2) Å, c = 15.915 (4) Å, β = 99.95 (2)°, Z = 4, R = 0.039), and was shown to have a distorted square-planar cis geometry. Complex 8 reacted with CO to form the carbonyl adduct, [Rh(PN)2(CO)]+ (9). The reaction of the tridentate ligand 2-[bis(diphenylphosphino)methyl]pyridine (PNP) with [Rh(CO)2Cl2]- under refluxing conditions of 2-methoxyethanol/toluene produced the 4-coordinate complex Rh(PN′)(CO)Cl (11). The ligand PN′ = 2-[(diphenylphosphino)methyl]pyridine resulted from P-C bond cleavage of PNP. The PN analogue of 11, Rh(PN)(CO)Cl (10), was also synthesized by reaction of [Rh(CO)2Cl2]-with PN in 2-methoxyethanol/toluene solution. Complexes 9-11 were characterized by IR and 31P NMR spectroscopy. The activities for the decarbonylation of benzaldehyde with use of 1(PF6) and 8(BF4) were found to be 9 and 10 turnovers/h, respectively, at 150°C in neat benzaldehyde, and their catalytic properties were studied. The results are discussed and compared to the catalytic activity and proposed mechanism of the decarbonylation reaction using [M(dppp)2]+ (M = Rh, Ir; dppp = 1,3-bis(diphenylphosphino)propane).

AB - Several new PN [1-(2-pyridyl)-2-(diphenylphosphino)ethane] complexes of rhodium and iridium have been synthesized. [Ir(PN)2]+ (1) was synthesized from [Ir(PN)(cod)]+ (cod = cyclooctadiene) and an excess of PN in acetone solution and characterized by IR, 1H NMR, and 31P NMR spectroscopy. 1 reacted with H2 in acetonitrile solution to form the cis-dihydride [Ir(PN)2(H)2]+ (2). Ir(PN)2(CO)Cl (3) and Ir(PN)(CO)Cl (4) were synthesized from the reaction of 2-methoxyethanol solutions of [Ir(CO)2Cl2]- with 2 and 1 equiv of PN, respectively. These four-coordinate square-planar complexes were characterized by IR and 31P NMR spectroscopy and by single-crystal X-ray analysis (3, monoclinic P21/a, a = 13.178 (2) Å, b = 13.579 (2) Å, c = 9.672 (2) Å, β = 93.84 (1)°, Z = 2, R = 0.025; 4-Et2O, triclinic P1, a = 11.079 (3) Å, b = 12.901 (3) Å, c = 8.377 (3) Å, α = 101.95 (3)°, β = 109.50 (3)°, γ = 73.01 (2)°, Z = 2, R = 0.025). In 3, both PN ligands are monodentate coordinated through the phosphorus atom. [Ir(PN)2(CO)]+ (5) was synthesized from 3 with KPF6 in acetone solution and characterized by IR and 31P NMR spectroscopy as a four-coordinate square-planar complex with one PN ligand bidentate and one monodentate bonded through the phosphorus atom. The reactivity of 5 with H2 and H+ was also examined. The reaction of PN with an acetone solution of [Rh(nbd)Cl]2 (nbd = norbornadiene) treated with AgPF6 produced a new chelated complex, [Rh(PN)2]PF6 (8(PF6)), which was characterized by IR and 31P NMR spectroscopy and by single-crystal X-ray diffraction (monoclinic P21/n, a = 10.714 (2) Å, 6 = 21.774 (2) Å, c = 15.915 (4) Å, β = 99.95 (2)°, Z = 4, R = 0.039), and was shown to have a distorted square-planar cis geometry. Complex 8 reacted with CO to form the carbonyl adduct, [Rh(PN)2(CO)]+ (9). The reaction of the tridentate ligand 2-[bis(diphenylphosphino)methyl]pyridine (PNP) with [Rh(CO)2Cl2]- under refluxing conditions of 2-methoxyethanol/toluene produced the 4-coordinate complex Rh(PN′)(CO)Cl (11). The ligand PN′ = 2-[(diphenylphosphino)methyl]pyridine resulted from P-C bond cleavage of PNP. The PN analogue of 11, Rh(PN)(CO)Cl (10), was also synthesized by reaction of [Rh(CO)2Cl2]-with PN in 2-methoxyethanol/toluene solution. Complexes 9-11 were characterized by IR and 31P NMR spectroscopy. The activities for the decarbonylation of benzaldehyde with use of 1(PF6) and 8(BF4) were found to be 9 and 10 turnovers/h, respectively, at 150°C in neat benzaldehyde, and their catalytic properties were studied. The results are discussed and compared to the catalytic activity and proposed mechanism of the decarbonylation reaction using [M(dppp)2]+ (M = Rh, Ir; dppp = 1,3-bis(diphenylphosphino)propane).

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