Formation of a Heterobimetallic Compound by Reductive Elimination of CH4 and Oxidative Cleavage of an Aryl-Phosphorus Bond in Reaction of trans-MeIr(CO)[P(p-tolyl)3]2 with HMoCp(CO)3: Crystal and Molecular Structures of CpMo(CO)2[μ-P(p-tolyl)2]Ir(p-tolyl)[P(p-tolyl)3](CO)2(Mo-Ir) and CpMo(CO)2[μ-P(p-tolyl)2]Ir(H)[P(p-tolyl)3](CO)2(Mo-Ir)

Jeffrey M. McFarland; Melvyn Rowen Churchill; Ronald F. See; Charles H. Lake; Jim D. Atwood

doi:10.1021/om00056a024

Formation of a Heterobimetallic Compound by Reductive Elimination of CH₄ and Oxidative Cleavage of an Aryl-Phosphorus Bond in Reaction of trans-MeIr(CO)[P(p-tolyl)₃]₂ with HMoCp(CO)₃: Crystal and Molecular Structures of CpMo(CO)₂[μ-P(p-tolyl)₂]Ir(p-tolyl)[P(p-tolyl)₃](CO)₂(Mo-Ir) and CpMo(CO)₂[μ-P(p-tolyl)₂]Ir(H)[P(p-tolyl)₃](CO)₂(Mo-Ir)

Jeffrey M. McFarland
, Melvyn Rowen Churchill
, Ronald F. See
, Charles H. Lake
, Jim D. Atwood

Chemistry

SUNY Buffalo

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

Reaction of HMoCp(CO)₃ with trans-MeIr(CO)[P(p-tolyl)₃]₂ results in quantitative elimination of CH₄ and formation of a heterobimetallic complex, Cp(CO)₂Mo[μ-P(p-tolyl)₂]Ir(p-tolyl)[P(p-tolyl)₃](CO)₂, by activation of the phosphorus-carbon bond. This complex has been fully characterized, including by X-ray crystallography. Cp(CO)₂Mo[μ-P(p-tolyl)₂]Ir(p-tolyl)[P(p-tolyl)₃](CO)₂(Mo-Ir) crystallizes in the centrosymmetric monoclinic space group P2₁/n (No. 14) with a = 13.108 (5) Å, b = 11.892 (5) Å, c = 30.165 (11) Å, β = 102.52 (3)°, V = 4590 (3) Å³, and Z = 4. Diffraction data (Mo Kα, 2θ = 5–45°) were collected with a Siemens R3m/V diffractometer and the structure was refined to R = 7.68% and R_w = 6.05% for all 6023 reflections (R = 3.62%, R_w = 4.63% for those 3586 reflections with F_o > 6.0σ(F_o)). The molecule contains a molybdenum-iridium bond (Mo -Ir = 2.976 (2) Å), which is bridged by a μ-P(p-tolyl)₂ ligand (Mo-P = 2.412 (3) and Ir-P = 2.376 (3) Å). The molybdenum atom is bonded to an η⁵-C₅H₆ ligand (Mo-C = 2.306 (11)-2.377 (11) Å) and two terminal carbonyl ligands (Mo-CO = 1.937 (10)-1.942 (15) Å); the iridium atom is bonded to mutually trans carbonyl ligands (Ir-CO = 1.899 (14)-1.907 (12) Å) and mutually cis P(p-tolyl)₃ and σ-(p-tolyl) ligands (Ir-P = 2.355 (3) and Ir-C(ipso) = 2.168 (10) Å). The heterobimetallic complex is surprisingly unreactive to CO, CH₃I, and PhC≡CPh; however, reaction with H₂ causes elimination of toluene and formation of a trihydride and a monohydride. Both have been separated and fully char acterized. These hydrides are fluxional at room temperature and appear to be reactive. The monohydride, CpMo(CO)₂[μ-P(p-tolyl)₂]Ir(H)[P(p-tolyl)₃](CO)₂(Mo-Ir), crystallizes in the centrosymmetric orthorhombic space group Pbca (No. 61) with a = 12.934 (2) Å, b = 23.890 (3) Å, c = 26.615 (3) Å, V = 8224 (2) Å³, and Z = 4. The structure was refined to R = 8.18% and R_w = 6.56% for all 5390 reflections (R = 3.41%, R_w = 3.59% for those 2861 reflections with F_o > 6.0σ(F_o)). This molecule has Mo(1)-Ir(1) = 2.957 (1) Å and a bridging μ-P(p-tolyl)₂ ligand associated with Mo-P = 2.391 (3) and Ir-P = 2.334 (3) Å. The molybdenum atom is bonded to an η⁶-C₅H₅ ligand (Mo-C = 2.283 (14)-2.383 (15) Å) and two terminal carbonyl ligands (Mo-CO = 1.940 (13)-1.953 (14) Å); the iridium atom is now bonded to mutually cis carbonyl ligands (Ir-CO = 1.899 (13)-1.912 (15) Å) and mutually cis P(p-tolyl)₃ and hydride ligands (Ir-P = 2.333 (3) Å and Ir-H = 1.67 (9) Å).

Original language	English
Pages (from-to)	3530-3537
Number of pages	8
Journal	Organometallics
Volume	10
Issue number	10
DOIs	https://doi.org/10.1021/om00056a024
State	Published - Oct 1 1991

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McFarland, J. M., Churchill, M. R., See, R. F., Lake, C. H., & Atwood, J. D. (1991). Formation of a Heterobimetallic Compound by Reductive Elimination of CH₄ and Oxidative Cleavage of an Aryl-Phosphorus Bond in Reaction of trans-MeIr(CO)[P(p-tolyl)₃]₂ with HMoCp(CO)₃: Crystal and Molecular Structures of CpMo(CO)₂[μ-P(p-tolyl)₂]Ir(p-tolyl)[P(p-tolyl)₃](CO)₂(Mo-Ir) and CpMo(CO)₂[μ-P(p-tolyl)₂]Ir(H)[P(p-tolyl)₃](CO)₂(Mo-Ir). Organometallics, 10(10), 3530-3537. https://doi.org/10.1021/om00056a024

McFarland, Jeffrey M. ; Churchill, Melvyn Rowen ; See, Ronald F. et al. / Formation of a Heterobimetallic Compound by Reductive Elimination of CH₄ and Oxidative Cleavage of an Aryl-Phosphorus Bond in Reaction of trans-MeIr(CO)[P(p-tolyl)₃]₂ with HMoCp(CO)₃ : Crystal and Molecular Structures of CpMo(CO)₂[μ-P(p-tolyl)₂]Ir(p-tolyl)[P(p-tolyl)₃](CO)₂(Mo-Ir) and CpMo(CO)₂[μ-P(p-tolyl)₂]Ir(H)[P(p-tolyl)₃](CO)₂(Mo-Ir). In: Organometallics. 1991 ; Vol. 10, No. 10. pp. 3530-3537.

@article{94257d826686404b90ccf2c5e10937b7,

title = "Formation of a Heterobimetallic Compound by Reductive Elimination of CH4 and Oxidative Cleavage of an Aryl-Phosphorus Bond in Reaction of trans-MeIr(CO)[P(p-tolyl)3]2 with HMoCp(CO)3: Crystal and Molecular Structures of CpMo(CO)2[μ-P(p-tolyl)2]Ir(p-tolyl)[P(p-tolyl)3](CO)2(Mo-Ir) and CpMo(CO)2[μ-P(p-tolyl)2]Ir(H)[P(p-tolyl)3](CO)2(Mo-Ir)",

abstract = "Reaction of HMoCp(CO)3 with trans-MeIr(CO)[P(p-tolyl)3]2 results in quantitative elimination of CH4 and formation of a heterobimetallic complex, Cp(CO)2Mo[μ-P(p-tolyl)2]Ir(p-tolyl)[P(p-tolyl)3](CO)2, by activation of the phosphorus-carbon bond. This complex has been fully characterized, including by X-ray crystallography. Cp(CO)2Mo[μ-P(p-tolyl)2]Ir(p-tolyl)[P(p-tolyl)3](CO)2(Mo-Ir) crystallizes in the centrosymmetric monoclinic space group P21/n (No. 14) with a = 13.108 (5) {\AA}, b = 11.892 (5) {\AA}, c = 30.165 (11) {\AA}, β = 102.52 (3)°, V = 4590 (3) {\AA}3, and Z = 4. Diffraction data (Mo Kα, 2θ = 5–45°) were collected with a Siemens R3m/V diffractometer and the structure was refined to R = 7.68\% and Rw = 6.05\% for all 6023 reflections (R = 3.62\%, Rw = 4.63\% for those 3586 reflections with Fo > 6.0σ(Fo)). The molecule contains a molybdenum-iridium bond (Mo -Ir = 2.976 (2) {\AA}), which is bridged by a μ-P(p-tolyl)2 ligand (Mo-P = 2.412 (3) and Ir-P = 2.376 (3) {\AA}). The molybdenum atom is bonded to an η5-C5H6 ligand (Mo-C = 2.306 (11)-2.377 (11) {\AA}) and two terminal carbonyl ligands (Mo-CO = 1.937 (10)-1.942 (15) {\AA}); the iridium atom is bonded to mutually trans carbonyl ligands (Ir-CO = 1.899 (14)-1.907 (12) {\AA}) and mutually cis P(p-tolyl)3 and σ-(p-tolyl) ligands (Ir-P = 2.355 (3) and Ir-C(ipso) = 2.168 (10) {\AA}). The heterobimetallic complex is surprisingly unreactive to CO, CH3I, and PhC≡CPh; however, reaction with H2 causes elimination of toluene and formation of a trihydride and a monohydride. Both have been separated and fully char acterized. These hydrides are fluxional at room temperature and appear to be reactive. The monohydride, CpMo(CO)2[μ-P(p-tolyl)2]Ir(H)[P(p-tolyl)3](CO)2(Mo-Ir), crystallizes in the centrosymmetric orthorhombic space group Pbca (No. 61) with a = 12.934 (2) {\AA}, b = 23.890 (3) {\AA}, c = 26.615 (3) {\AA}, V = 8224 (2) {\AA}3, and Z = 4. The structure was refined to R = 8.18\% and Rw = 6.56\% for all 5390 reflections (R = 3.41\%, Rw = 3.59\% for those 2861 reflections with Fo > 6.0σ(Fo)). This molecule has Mo(1)-Ir(1) = 2.957 (1) {\AA} and a bridging μ-P(p-tolyl)2 ligand associated with Mo-P = 2.391 (3) and Ir-P = 2.334 (3) {\AA}. The molybdenum atom is bonded to an η6-C5H5 ligand (Mo-C = 2.283 (14)-2.383 (15) {\AA}) and two terminal carbonyl ligands (Mo-CO = 1.940 (13)-1.953 (14) {\AA}); the iridium atom is now bonded to mutually cis carbonyl ligands (Ir-CO = 1.899 (13)-1.912 (15) {\AA}) and mutually cis P(p-tolyl)3 and hydride ligands (Ir-P = 2.333 (3) {\AA} and Ir-H = 1.67 (9) {\AA}).",

author = "McFarland, \{Jeffrey M.\} and Churchill, \{Melvyn Rowen\} and See, \{Ronald F.\} and Lake, \{Charles H.\} and Atwood, \{Jim D.\}",

year = "1991",

month = oct,

day = "1",

doi = "10.1021/om00056a024",

language = "English",

volume = "10",

pages = "3530--3537",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "10",

}

McFarland, JM, Churchill, MR, See, RF, Lake, CH & Atwood, JD 1991, 'Formation of a Heterobimetallic Compound by Reductive Elimination of CH₄ and Oxidative Cleavage of an Aryl-Phosphorus Bond in Reaction of trans-MeIr(CO)[P(p-tolyl)₃]₂ with HMoCp(CO)₃: Crystal and Molecular Structures of CpMo(CO)₂[μ-P(p-tolyl)₂]Ir(p-tolyl)[P(p-tolyl)₃](CO)₂(Mo-Ir) and CpMo(CO)₂[μ-P(p-tolyl)₂]Ir(H)[P(p-tolyl)₃](CO)₂(Mo-Ir)', Organometallics, vol. 10, no. 10, pp. 3530-3537. https://doi.org/10.1021/om00056a024

Formation of a Heterobimetallic Compound by Reductive Elimination of CH₄ and Oxidative Cleavage of an Aryl-Phosphorus Bond in Reaction of trans-MeIr(CO)[P(p-tolyl)₃]₂ with HMoCp(CO)₃: Crystal and Molecular Structures of CpMo(CO)₂[μ-P(p-tolyl)₂]Ir(p-tolyl)[P(p-tolyl)₃](CO)₂(Mo-Ir) and CpMo(CO)₂[μ-P(p-tolyl)₂]Ir(H)[P(p-tolyl)₃](CO)₂(Mo-Ir). / McFarland, Jeffrey M.; Churchill, Melvyn Rowen; See, Ronald F. et al.
In: Organometallics, Vol. 10, No. 10, 01.10.1991, p. 3530-3537.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Formation of a Heterobimetallic Compound by Reductive Elimination of CH4 and Oxidative Cleavage of an Aryl-Phosphorus Bond in Reaction of trans-MeIr(CO)[P(p-tolyl)3]2 with HMoCp(CO)3

T2 - Crystal and Molecular Structures of CpMo(CO)2[μ-P(p-tolyl)2]Ir(p-tolyl)[P(p-tolyl)3](CO)2(Mo-Ir) and CpMo(CO)2[μ-P(p-tolyl)2]Ir(H)[P(p-tolyl)3](CO)2(Mo-Ir)

AU - McFarland, Jeffrey M.

AU - Churchill, Melvyn Rowen

AU - See, Ronald F.

AU - Lake, Charles H.

AU - Atwood, Jim D.

PY - 1991/10/1

Y1 - 1991/10/1

N2 - Reaction of HMoCp(CO)3 with trans-MeIr(CO)[P(p-tolyl)3]2 results in quantitative elimination of CH4 and formation of a heterobimetallic complex, Cp(CO)2Mo[μ-P(p-tolyl)2]Ir(p-tolyl)[P(p-tolyl)3](CO)2, by activation of the phosphorus-carbon bond. This complex has been fully characterized, including by X-ray crystallography. Cp(CO)2Mo[μ-P(p-tolyl)2]Ir(p-tolyl)[P(p-tolyl)3](CO)2(Mo-Ir) crystallizes in the centrosymmetric monoclinic space group P21/n (No. 14) with a = 13.108 (5) Å, b = 11.892 (5) Å, c = 30.165 (11) Å, β = 102.52 (3)°, V = 4590 (3) Å3, and Z = 4. Diffraction data (Mo Kα, 2θ = 5–45°) were collected with a Siemens R3m/V diffractometer and the structure was refined to R = 7.68% and Rw = 6.05% for all 6023 reflections (R = 3.62%, Rw = 4.63% for those 3586 reflections with Fo > 6.0σ(Fo)). The molecule contains a molybdenum-iridium bond (Mo -Ir = 2.976 (2) Å), which is bridged by a μ-P(p-tolyl)2 ligand (Mo-P = 2.412 (3) and Ir-P = 2.376 (3) Å). The molybdenum atom is bonded to an η5-C5H6 ligand (Mo-C = 2.306 (11)-2.377 (11) Å) and two terminal carbonyl ligands (Mo-CO = 1.937 (10)-1.942 (15) Å); the iridium atom is bonded to mutually trans carbonyl ligands (Ir-CO = 1.899 (14)-1.907 (12) Å) and mutually cis P(p-tolyl)3 and σ-(p-tolyl) ligands (Ir-P = 2.355 (3) and Ir-C(ipso) = 2.168 (10) Å). The heterobimetallic complex is surprisingly unreactive to CO, CH3I, and PhC≡CPh; however, reaction with H2 causes elimination of toluene and formation of a trihydride and a monohydride. Both have been separated and fully char acterized. These hydrides are fluxional at room temperature and appear to be reactive. The monohydride, CpMo(CO)2[μ-P(p-tolyl)2]Ir(H)[P(p-tolyl)3](CO)2(Mo-Ir), crystallizes in the centrosymmetric orthorhombic space group Pbca (No. 61) with a = 12.934 (2) Å, b = 23.890 (3) Å, c = 26.615 (3) Å, V = 8224 (2) Å3, and Z = 4. The structure was refined to R = 8.18% and Rw = 6.56% for all 5390 reflections (R = 3.41%, Rw = 3.59% for those 2861 reflections with Fo > 6.0σ(Fo)). This molecule has Mo(1)-Ir(1) = 2.957 (1) Å and a bridging μ-P(p-tolyl)2 ligand associated with Mo-P = 2.391 (3) and Ir-P = 2.334 (3) Å. The molybdenum atom is bonded to an η6-C5H5 ligand (Mo-C = 2.283 (14)-2.383 (15) Å) and two terminal carbonyl ligands (Mo-CO = 1.940 (13)-1.953 (14) Å); the iridium atom is now bonded to mutually cis carbonyl ligands (Ir-CO = 1.899 (13)-1.912 (15) Å) and mutually cis P(p-tolyl)3 and hydride ligands (Ir-P = 2.333 (3) Å and Ir-H = 1.67 (9) Å).

AB - Reaction of HMoCp(CO)3 with trans-MeIr(CO)[P(p-tolyl)3]2 results in quantitative elimination of CH4 and formation of a heterobimetallic complex, Cp(CO)2Mo[μ-P(p-tolyl)2]Ir(p-tolyl)[P(p-tolyl)3](CO)2, by activation of the phosphorus-carbon bond. This complex has been fully characterized, including by X-ray crystallography. Cp(CO)2Mo[μ-P(p-tolyl)2]Ir(p-tolyl)[P(p-tolyl)3](CO)2(Mo-Ir) crystallizes in the centrosymmetric monoclinic space group P21/n (No. 14) with a = 13.108 (5) Å, b = 11.892 (5) Å, c = 30.165 (11) Å, β = 102.52 (3)°, V = 4590 (3) Å3, and Z = 4. Diffraction data (Mo Kα, 2θ = 5–45°) were collected with a Siemens R3m/V diffractometer and the structure was refined to R = 7.68% and Rw = 6.05% for all 6023 reflections (R = 3.62%, Rw = 4.63% for those 3586 reflections with Fo > 6.0σ(Fo)). The molecule contains a molybdenum-iridium bond (Mo -Ir = 2.976 (2) Å), which is bridged by a μ-P(p-tolyl)2 ligand (Mo-P = 2.412 (3) and Ir-P = 2.376 (3) Å). The molybdenum atom is bonded to an η5-C5H6 ligand (Mo-C = 2.306 (11)-2.377 (11) Å) and two terminal carbonyl ligands (Mo-CO = 1.937 (10)-1.942 (15) Å); the iridium atom is bonded to mutually trans carbonyl ligands (Ir-CO = 1.899 (14)-1.907 (12) Å) and mutually cis P(p-tolyl)3 and σ-(p-tolyl) ligands (Ir-P = 2.355 (3) and Ir-C(ipso) = 2.168 (10) Å). The heterobimetallic complex is surprisingly unreactive to CO, CH3I, and PhC≡CPh; however, reaction with H2 causes elimination of toluene and formation of a trihydride and a monohydride. Both have been separated and fully char acterized. These hydrides are fluxional at room temperature and appear to be reactive. The monohydride, CpMo(CO)2[μ-P(p-tolyl)2]Ir(H)[P(p-tolyl)3](CO)2(Mo-Ir), crystallizes in the centrosymmetric orthorhombic space group Pbca (No. 61) with a = 12.934 (2) Å, b = 23.890 (3) Å, c = 26.615 (3) Å, V = 8224 (2) Å3, and Z = 4. The structure was refined to R = 8.18% and Rw = 6.56% for all 5390 reflections (R = 3.41%, Rw = 3.59% for those 2861 reflections with Fo > 6.0σ(Fo)). This molecule has Mo(1)-Ir(1) = 2.957 (1) Å and a bridging μ-P(p-tolyl)2 ligand associated with Mo-P = 2.391 (3) and Ir-P = 2.334 (3) Å. The molybdenum atom is bonded to an η6-C5H5 ligand (Mo-C = 2.283 (14)-2.383 (15) Å) and two terminal carbonyl ligands (Mo-CO = 1.940 (13)-1.953 (14) Å); the iridium atom is now bonded to mutually cis carbonyl ligands (Ir-CO = 1.899 (13)-1.912 (15) Å) and mutually cis P(p-tolyl)3 and hydride ligands (Ir-P = 2.333 (3) Å and Ir-H = 1.67 (9) Å).

UR - https://www.scopus.com/pages/publications/0347534504

U2 - 10.1021/om00056a024

DO - 10.1021/om00056a024

M3 - Article

AN - SCOPUS:0347534504

SN - 0276-7333

VL - 10

SP - 3530

EP - 3537

JO - Organometallics

JF - Organometallics

IS - 10

ER -

McFarland JM, Churchill MR, See RF, Lake CH, Atwood JD. Formation of a Heterobimetallic Compound by Reductive Elimination of CH₄ and Oxidative Cleavage of an Aryl-Phosphorus Bond in Reaction of trans-MeIr(CO)[P(p-tolyl)₃]₂ with HMoCp(CO)₃: Crystal and Molecular Structures of CpMo(CO)₂[μ-P(p-tolyl)₂]Ir(p-tolyl)[P(p-tolyl)₃](CO)₂(Mo-Ir) and CpMo(CO)₂[μ-P(p-tolyl)₂]Ir(H)[P(p-tolyl)₃](CO)₂(Mo-Ir). Organometallics. 1991 Oct 1;10(10):3530-3537. doi: 10.1021/om00056a024

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