Formation of carboncarbon bonds on di(organo)iridium complexes, rr′Ir(CO)(PPh3)2X (R,R′ = Me, Ph, CH2Ph, C(O)CH3; X = Cl, I) and the crystal structure of cis,cis,trans-[Ir(CH3)2(CO)2(PPh3)2+][CF3SO3-]

Melvyn Rowen Churchill; James C. Fettinger; Thomas S. Janik; Wayne M. Rees; Jeffrey S. Thompson; Sharon Tomaszewski; Jim D. Atwood

doi:10.1016/0022-328X(87)80372-8

Formation of carboncarbon bonds on di(organo)iridium complexes, rr′Ir(CO)(PPh₃)₂X (R,R′ = Me, Ph, CH₂Ph, C(O)CH₃; X = Cl, I) and the crystal structure of cis,cis,trans-[Ir(CH₃)₂(CO)₂(PPh₃)₂⁺][CF₃SO₃^-]

Melvyn Rowen Churchill
, James C. Fettinger
, Thomas S. Janik
, Wayne M. Rees
, Jeffrey S. Thompson
, Sharon Tomaszewski
, Jim D. Atwood

Chemistry

SUNY Buffalo

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

12 Scopus citations

Abstract

The reactions of RX with trans-R′Ir(CO(PPh₃)₂ are reported. Addition of CH₃C(O)Cl to trans-CH₃Ir(CO)(PPh₃)₂ leads to acetone; addition of CH₃I to trans-PhIr(CO)(PPh₃)₂ leads to toluene; and addition of CH₃I to trans-C₆H₅CH₂Ir(CO)(PPh₃)₂ leads to ethylbenzene. Reaction of C₂H₅Br with trans-CH₃Ir(CO)(PPh₃)₂ leads to CH₄ and C₂H₄. The addition of CH₃I to trans-CH₃Ir(CO)(PPh₃)₂ leads to Ir(CH₃)₂Ir(CO)(PPh₃)₂I from which Ir(CH₃)₂(CO)-(PPh₃)₂⁺ and Ir(CH₃)₂(CO)₂(PPh₃)₂⁺ can be prepared. These dimethyl complexes do not undergo reductive elimination of ethane, acetone or diacetyl under a variety of conditions (CH₄ and C₂H₆ are formed at decomposition). Thus for these complexes the charge, the presence of a free coordination site and the cis stereochemistry do not facilitate reductive elimination reactions. To ascertain that no structural features were preventing reductive elimination from the dimethyl complex we have examined the structure of cis,cis,trans-[Ir(CH₃)₂(CO)₂(PPh₃)₂⁺][CF₃SO₃^-]. This crystallizes in the centrosymmetric triclinic space group P1 (C_i¹; No. 2) with a 11.708(2), b 11.738(2) c 14.702(2) Å, α 87.544(13), β 79.181(14), γ 76.963(15)°, V 1933.4(6) Å³ and D(calc'd) 1.64 g cm^-3 for mol. wt. 951.9 and Z = 2. x-ray diffraction data (Mo-K_α, 2θ 4.5-50.0°) were collected with a Syntex P2₁ automated four-circle diffractometer and the structure was refined to R 3.5% for all 6835 reflections (R 2.9% for those 6133 reflections with |F₀| > 6σ(|F₀|)). The central d⁶ iridium(III) ion has a slightly distorted octahedral stereochemistry, with Ir-CO 1.943(5) and 1.956(5) Å, Ir-CH₃ 2.152(5) and 2.155(5) Å and Ir-PPh₃ 2.391(1) and 2.400(1) Å; interligand angles include OC-Ir_CO 102.09(20), CH₃-Ir-CH₃ 89.70(19) and PPh₃-Ir-PPh₃ 174.68(4)°.

Original language	English
Pages (from-to)	233-246
Number of pages	14
Journal	Journal of Organometallic Chemistry
Volume	323
Issue number	2
DOIs	https://doi.org/10.1016/0022-328X(87)80372-8
State	Published - Apr 21 1987

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Churchill, M. R., Fettinger, J. C., Janik, T. S., Rees, W. M., Thompson, J. S., Tomaszewski, S., & Atwood, J. D. (1987). Formation of carboncarbon bonds on di(organo)iridium complexes, rr′Ir(CO)(PPh₃)₂X (R,R′ = Me, Ph, CH₂Ph, C(O)CH₃; X = Cl, I) and the crystal structure of cis,cis,trans-[Ir(CH₃)₂(CO)₂(PPh₃)₂⁺][CF₃SO₃^-]. Journal of Organometallic Chemistry, 323(2), 233-246. https://doi.org/10.1016/0022-328X(87)80372-8

@article{4c963d19791a464ebefbd50d0211dd23,

title = "Formation of carboncarbon bonds on di(organo)iridium complexes, rr′Ir(CO)(PPh3)2X (R,R′ = Me, Ph, CH2Ph, C(O)CH3; X = Cl, I) and the crystal structure of cis,cis,trans-[Ir(CH3)2(CO)2(PPh3)2+][CF3SO3-]",

abstract = "The reactions of RX with trans-R′Ir(CO(PPh3)2 are reported. Addition of CH3C(O)Cl to trans-CH3Ir(CO)(PPh3)2 leads to acetone; addition of CH3I to trans-PhIr(CO)(PPh3)2 leads to toluene; and addition of CH3I to trans-C6H5CH2Ir(CO)(PPh3)2 leads to ethylbenzene. Reaction of C2H5Br with trans-CH3Ir(CO)(PPh3)2 leads to CH4 and C2H4. The addition of CH3I to trans-CH3Ir(CO)(PPh3)2 leads to Ir(CH3)2Ir(CO)(PPh3)2I from which Ir(CH3)2(CO)-(PPh3)2+ and Ir(CH3)2(CO)2(PPh3)2+ can be prepared. These dimethyl complexes do not undergo reductive elimination of ethane, acetone or diacetyl under a variety of conditions (CH4 and C2H6 are formed at decomposition). Thus for these complexes the charge, the presence of a free coordination site and the cis stereochemistry do not facilitate reductive elimination reactions. To ascertain that no structural features were preventing reductive elimination from the dimethyl complex we have examined the structure of cis,cis,trans-[Ir(CH3)2(CO)2(PPh3)2+][CF3SO3-]. This crystallizes in the centrosymmetric triclinic space group P1 (Ci1; No. 2) with a 11.708(2), b 11.738(2) c 14.702(2) {\AA}, α 87.544(13), β 79.181(14), γ 76.963(15)°, V 1933.4(6) {\AA}3 and D(calc'd) 1.64 g cm-3 for mol. wt. 951.9 and Z = 2. x-ray diffraction data (Mo-Kα, 2θ 4.5-50.0°) were collected with a Syntex P21 automated four-circle diffractometer and the structure was refined to R 3.5\% for all 6835 reflections (R 2.9\% for those 6133 reflections with |F0| > 6σ(|F0|)). The central d6 iridium(III) ion has a slightly distorted octahedral stereochemistry, with Ir-CO 1.943(5) and 1.956(5) {\AA}, Ir-CH3 2.152(5) and 2.155(5) {\AA} and Ir-PPh3 2.391(1) and 2.400(1) {\AA}; interligand angles include OC-Ir\_CO 102.09(20), CH3-Ir-CH3 89.70(19) and PPh3-Ir-PPh3 174.68(4)°.",

author = "Churchill, \{Melvyn Rowen\} and Fettinger, \{James C.\} and Janik, \{Thomas S.\} and Rees, \{Wayne M.\} and Thompson, \{Jeffrey S.\} and Sharon Tomaszewski and Atwood, \{Jim D.\}",

year = "1987",

month = apr,

day = "21",

doi = "10.1016/0022-328X(87)80372-8",

language = "English",

volume = "323",

pages = "233--246",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "2",

}

Churchill, MR, Fettinger, JC, Janik, TS, Rees, WM, Thompson, JS, Tomaszewski, S & Atwood, JD 1987, 'Formation of carboncarbon bonds on di(organo)iridium complexes, rr′Ir(CO)(PPh₃)₂X (R,R′ = Me, Ph, CH₂Ph, C(O)CH₃; X = Cl, I) and the crystal structure of cis,cis,trans-[Ir(CH₃)₂(CO)₂(PPh₃)₂⁺][CF₃SO₃^-]', Journal of Organometallic Chemistry, vol. 323, no. 2, pp. 233-246. https://doi.org/10.1016/0022-328X(87)80372-8

Formation of carboncarbon bonds on di(organo)iridium complexes, rr′Ir(CO)(PPh₃)₂X (R,R′ = Me, Ph, CH₂Ph, C(O)CH₃; X = Cl, I) and the crystal structure of cis,cis,trans-[Ir(CH₃)₂(CO)₂(PPh₃)₂⁺][CF₃SO₃^-]. / Churchill, Melvyn Rowen; Fettinger, James C.; Janik, Thomas S. et al.
In: Journal of Organometallic Chemistry, Vol. 323, No. 2, 21.04.1987, p. 233-246.

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

TY - JOUR

T1 - Formation of carboncarbon bonds on di(organo)iridium complexes, rr′Ir(CO)(PPh3)2X (R,R′ = Me, Ph, CH2Ph, C(O)CH3; X = Cl, I) and the crystal structure of cis,cis,trans-[Ir(CH3)2(CO)2(PPh3)2+][CF3SO3-]

AU - Churchill, Melvyn Rowen

AU - Fettinger, James C.

AU - Janik, Thomas S.

AU - Rees, Wayne M.

AU - Thompson, Jeffrey S.

AU - Tomaszewski, Sharon

AU - Atwood, Jim D.

PY - 1987/4/21

Y1 - 1987/4/21

N2 - The reactions of RX with trans-R′Ir(CO(PPh3)2 are reported. Addition of CH3C(O)Cl to trans-CH3Ir(CO)(PPh3)2 leads to acetone; addition of CH3I to trans-PhIr(CO)(PPh3)2 leads to toluene; and addition of CH3I to trans-C6H5CH2Ir(CO)(PPh3)2 leads to ethylbenzene. Reaction of C2H5Br with trans-CH3Ir(CO)(PPh3)2 leads to CH4 and C2H4. The addition of CH3I to trans-CH3Ir(CO)(PPh3)2 leads to Ir(CH3)2Ir(CO)(PPh3)2I from which Ir(CH3)2(CO)-(PPh3)2+ and Ir(CH3)2(CO)2(PPh3)2+ can be prepared. These dimethyl complexes do not undergo reductive elimination of ethane, acetone or diacetyl under a variety of conditions (CH4 and C2H6 are formed at decomposition). Thus for these complexes the charge, the presence of a free coordination site and the cis stereochemistry do not facilitate reductive elimination reactions. To ascertain that no structural features were preventing reductive elimination from the dimethyl complex we have examined the structure of cis,cis,trans-[Ir(CH3)2(CO)2(PPh3)2+][CF3SO3-]. This crystallizes in the centrosymmetric triclinic space group P1 (Ci1; No. 2) with a 11.708(2), b 11.738(2) c 14.702(2) Å, α 87.544(13), β 79.181(14), γ 76.963(15)°, V 1933.4(6) Å3 and D(calc'd) 1.64 g cm-3 for mol. wt. 951.9 and Z = 2. x-ray diffraction data (Mo-Kα, 2θ 4.5-50.0°) were collected with a Syntex P21 automated four-circle diffractometer and the structure was refined to R 3.5% for all 6835 reflections (R 2.9% for those 6133 reflections with |F0| > 6σ(|F0|)). The central d6 iridium(III) ion has a slightly distorted octahedral stereochemistry, with Ir-CO 1.943(5) and 1.956(5) Å, Ir-CH3 2.152(5) and 2.155(5) Å and Ir-PPh3 2.391(1) and 2.400(1) Å; interligand angles include OC-Ir_CO 102.09(20), CH3-Ir-CH3 89.70(19) and PPh3-Ir-PPh3 174.68(4)°.

AB - The reactions of RX with trans-R′Ir(CO(PPh3)2 are reported. Addition of CH3C(O)Cl to trans-CH3Ir(CO)(PPh3)2 leads to acetone; addition of CH3I to trans-PhIr(CO)(PPh3)2 leads to toluene; and addition of CH3I to trans-C6H5CH2Ir(CO)(PPh3)2 leads to ethylbenzene. Reaction of C2H5Br with trans-CH3Ir(CO)(PPh3)2 leads to CH4 and C2H4. The addition of CH3I to trans-CH3Ir(CO)(PPh3)2 leads to Ir(CH3)2Ir(CO)(PPh3)2I from which Ir(CH3)2(CO)-(PPh3)2+ and Ir(CH3)2(CO)2(PPh3)2+ can be prepared. These dimethyl complexes do not undergo reductive elimination of ethane, acetone or diacetyl under a variety of conditions (CH4 and C2H6 are formed at decomposition). Thus for these complexes the charge, the presence of a free coordination site and the cis stereochemistry do not facilitate reductive elimination reactions. To ascertain that no structural features were preventing reductive elimination from the dimethyl complex we have examined the structure of cis,cis,trans-[Ir(CH3)2(CO)2(PPh3)2+][CF3SO3-]. This crystallizes in the centrosymmetric triclinic space group P1 (Ci1; No. 2) with a 11.708(2), b 11.738(2) c 14.702(2) Å, α 87.544(13), β 79.181(14), γ 76.963(15)°, V 1933.4(6) Å3 and D(calc'd) 1.64 g cm-3 for mol. wt. 951.9 and Z = 2. x-ray diffraction data (Mo-Kα, 2θ 4.5-50.0°) were collected with a Syntex P21 automated four-circle diffractometer and the structure was refined to R 3.5% for all 6835 reflections (R 2.9% for those 6133 reflections with |F0| > 6σ(|F0|)). The central d6 iridium(III) ion has a slightly distorted octahedral stereochemistry, with Ir-CO 1.943(5) and 1.956(5) Å, Ir-CH3 2.152(5) and 2.155(5) Å and Ir-PPh3 2.391(1) and 2.400(1) Å; interligand angles include OC-Ir_CO 102.09(20), CH3-Ir-CH3 89.70(19) and PPh3-Ir-PPh3 174.68(4)°.

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DO - 10.1016/0022-328X(87)80372-8

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