Carbonylation of Iridium(I) and Iridium(III) Complexes, trans-Ir(CO)(R)(P(p-tolyl)3)2 (R = Me, OMe, OCH2Ph, OC6H4Me, OH) and Ir(CO)(Me)(SO4)(P(p-tolyl)3)2, and Facile Elimination of Hard Ligands: Crystal and Molecular Structures of Ir(CO)(Me)(SO4)(P(p-tolyl)3)2 and [Ir(CO)3(P(p-tolyl)3)2][HSO4]

Sherri L. Randall; Cynthia A. Miller; Ronald F. See; Melvyn Rowen Churchill; Thomas S. Janik; Charles H. Lake; Jim D. Atwood

doi:10.1021/om00024a060

Carbonylation of Iridium(I) and Iridium(III) Complexes, trans-Ir(CO)(R)(P(p-tolyl)₃)₂ (R = Me, OMe, OCH₂Ph, OC₆H₄Me, OH) and Ir(CO)(Me)(SO₄)(P(p-tolyl)₃)₂, and Facile Elimination of Hard Ligands: Crystal and Molecular Structures of Ir(CO)(Me)(SO₄)(P(p-tolyl)₃)₂ and [Ir(CO)₃(P(p-tolyl)₃)₂][HSO₄]

Sherri L. Randall
, Cynthia A. Miller
, Ronald F. See
, Melvyn Rowen Churchill
, Thomas S. Janik
, Charles H. Lake
, Jim D. Atwood

Chemistry

SUNY Buffalo

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

18 Scopus citations

Abstract

Carbonylation of several iridium(I) complexes, trans-Ir(CO)(R)(P(p-tolyl)₃)₂ lead to products Ir(CO)₂(CO)R)(P(p-tolyl)₃)₂, R = Me, OCH₂Ph; and Ir₂(CO)₆(P(p-tolyl)₃)₂, R = OH, OMe, and OC₆H₄Me) that depend on the nature of the R group. Carbonylation of the iridium(III) complex, Ir(CO)(Me)(SO₄)(P(p-tolyl)₃)₂ leads to two iridium products, [Ir(CO)₃(P(p-tolyl)₃)₂⁺] and Ir(CO)₃(C(O)Me)(P(p-tolyl)₃)₂ by two different pathways. Structures of Ir(CO)(Me)(SO₄)- (P(p-tolyl)₃)₂ and [Ir(CO)₃(P(p-tolyl)₃)₂][HSO₄] were determined to assist in the interpretation. The complex Ir(CO)(Me)(SO₄)(P(p-tolyl)₃)₂ crystallizes in the orthorhombic space group Pbcn with a = 18.237(3), b = 12.572(2), c = 18.584(2) Å, V = 4260.9(11) Å3 and Z = 4. The structure was refined to R = 1.98% for 1640 reflections with F > 6σ(F). The molecule lies on a site of C₂ symmetry, necessitating a disorder of carbonyl and methyl ligands. Bond distances around the octahedral iridium(III) center include Ir-CO = 1.823(13), Ir-CH₃ = 2.127(14), Ir-–P= 2.398(1) and Ir–O(SO₄) = 2.119(4) Å. The species [Ir(CO)₃(P(p-tolyl)₃)₂][HSO₄] crystallizes in the monoclinic space group P2₁/n with a = 11.490(2), b = 12.255(3), c = 30.873(7) Å, β = 92.826(17)°, V = 4342.0(15) Å₃ and Z = 4. The structure was refined to R = 6.09% for 2591 reflections with F > 6σ(F). The Ir(CO)₃P₂ core of the cation has a geometry slightly distorted from D_3h symmetry, with Ir–P = 2.363(5) and 2.374(5) Å and Ir-CO = 1.921(21)− 2.012(28) Å. The HSO₄⁻ anion undergoes substantial librational motion (or is disordered) and is associated with S–O distances ranging from 1.31(4) through 1.49(3) Å.

Original language	English
Pages (from-to)	5088-5095
Number of pages	8
Journal	Organometallics
Volume	13
Issue number	12
DOIs	https://doi.org/10.1021/om00024a060
State	Published - Dec 1 1994

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Randall, S. L., Miller, C. A., See, R. F., Churchill, M. R., Janik, T. S., Lake, C. H., & Atwood, J. D. (1994). Carbonylation of Iridium(I) and Iridium(III) Complexes, trans-Ir(CO)(R)(P(p-tolyl)₃)₂ (R = Me, OMe, OCH₂Ph, OC₆H₄Me, OH) and Ir(CO)(Me)(SO₄)(P(p-tolyl)₃)₂, and Facile Elimination of Hard Ligands: Crystal and Molecular Structures of Ir(CO)(Me)(SO₄)(P(p-tolyl)₃)₂ and [Ir(CO)₃(P(p-tolyl)₃)₂][HSO₄]. Organometallics, 13(12), 5088-5095. https://doi.org/10.1021/om00024a060

Randall, Sherri L. ; Miller, Cynthia A. ; See, Ronald F. et al. / Carbonylation of Iridium(I) and Iridium(III) Complexes, trans-Ir(CO)(R)(P(p-tolyl)₃)₂ (R = Me, OMe, OCH₂Ph, OC₆H₄Me, OH) and Ir(CO)(Me)(SO₄)(P(p-tolyl)₃)₂, and Facile Elimination of Hard Ligands : Crystal and Molecular Structures of Ir(CO)(Me)(SO₄)(P(p-tolyl)₃)₂ and [Ir(CO)₃(P(p-tolyl)₃)₂][HSO₄]. In: Organometallics. 1994 ; Vol. 13, No. 12. pp. 5088-5095.

@article{0ea4e4d09a5d4857a0392e1e91b6e90a,

title = "Carbonylation of Iridium(I) and Iridium(III) Complexes, trans-Ir(CO)(R)(P(p-tolyl)3)2 (R = Me, OMe, OCH2Ph, OC6H4Me, OH) and Ir(CO)(Me)(SO4)(P(p-tolyl)3)2, and Facile Elimination of Hard Ligands: Crystal and Molecular Structures of Ir(CO)(Me)(SO4)(P(p-tolyl)3)2 and [Ir(CO)3(P(p-tolyl)3)2][HSO4]",

abstract = "Carbonylation of several iridium(I) complexes, trans-Ir(CO)(R)(P(p-tolyl)3)2 lead to products Ir(CO)2(CO)R)(P(p-tolyl)3)2, R = Me, OCH2Ph; and Ir2(CO)6(P(p-tolyl)3)2, R = OH, OMe, and OC6H4Me) that depend on the nature of the R group. Carbonylation of the iridium(III) complex, Ir(CO)(Me)(SO4)(P(p-tolyl)3)2 leads to two iridium products, [Ir(CO)3(P(p-tolyl)3)2+] and Ir(CO)3(C(O)Me)(P(p-tolyl)3)2 by two different pathways. Structures of Ir(CO)(Me)(SO4)- (P(p-tolyl)3)2 and [Ir(CO)3(P(p-tolyl)3)2][HSO4] were determined to assist in the interpretation. The complex Ir(CO)(Me)(SO4)(P(p-tolyl)3)2 crystallizes in the orthorhombic space group Pbcn with a = 18.237(3), b = 12.572(2), c = 18.584(2) {\AA}, V = 4260.9(11) {\AA}3 and Z = 4. The structure was refined to R = 1.98\% for 1640 reflections with F > 6σ(F). The molecule lies on a site of C2 symmetry, necessitating a disorder of carbonyl and methyl ligands. Bond distances around the octahedral iridium(III) center include Ir-CO = 1.823(13), Ir-CH3 = 2.127(14), Ir-–P= 2.398(1) and Ir–O(SO4) = 2.119(4) {\AA}. The species [Ir(CO)3(P(p-tolyl)3)2][HSO4] crystallizes in the monoclinic space group P21/n with a = 11.490(2), b = 12.255(3), c = 30.873(7) {\AA}, β = 92.826(17)°, V = 4342.0(15) {\AA}3 and Z = 4. The structure was refined to R = 6.09\% for 2591 reflections with F > 6σ(F). The Ir(CO)3P2 core of the cation has a geometry slightly distorted from D3h symmetry, with Ir–P = 2.363(5) and 2.374(5) {\AA} and Ir-CO = 1.921(21)− 2.012(28) {\AA}. The HSO4− anion undergoes substantial librational motion (or is disordered) and is associated with S–O distances ranging from 1.31(4) through 1.49(3) {\AA}.",

author = "Randall, \{Sherri L.\} and Miller, \{Cynthia A.\} and See, \{Ronald F.\} and Churchill, \{Melvyn Rowen\} and Janik, \{Thomas S.\} and Lake, \{Charles H.\} and Atwood, \{Jim D.\}",

year = "1994",

month = dec,

day = "1",

doi = "10.1021/om00024a060",

language = "English",

volume = "13",

pages = "5088--5095",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "12",

}

Randall, SL, Miller, CA, See, RF, Churchill, MR, Janik, TS, Lake, CH & Atwood, JD 1994, 'Carbonylation of Iridium(I) and Iridium(III) Complexes, trans-Ir(CO)(R)(P(p-tolyl)₃)₂ (R = Me, OMe, OCH₂Ph, OC₆H₄Me, OH) and Ir(CO)(Me)(SO₄)(P(p-tolyl)₃)₂, and Facile Elimination of Hard Ligands: Crystal and Molecular Structures of Ir(CO)(Me)(SO₄)(P(p-tolyl)₃)₂ and [Ir(CO)₃(P(p-tolyl)₃)₂][HSO₄]', Organometallics, vol. 13, no. 12, pp. 5088-5095. https://doi.org/10.1021/om00024a060

Carbonylation of Iridium(I) and Iridium(III) Complexes, trans-Ir(CO)(R)(P(p-tolyl)₃)₂ (R = Me, OMe, OCH₂Ph, OC₆H₄Me, OH) and Ir(CO)(Me)(SO₄)(P(p-tolyl)₃)₂, and Facile Elimination of Hard Ligands: Crystal and Molecular Structures of Ir(CO)(Me)(SO₄)(P(p-tolyl)₃)₂ and [Ir(CO)₃(P(p-tolyl)₃)₂][HSO₄]. / Randall, Sherri L.; Miller, Cynthia A.; See, Ronald F. et al.
In: Organometallics, Vol. 13, No. 12, 01.12.1994, p. 5088-5095.

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

TY - JOUR

T1 - Carbonylation of Iridium(I) and Iridium(III) Complexes, trans-Ir(CO)(R)(P(p-tolyl)3)2 (R = Me, OMe, OCH2Ph, OC6H4Me, OH) and Ir(CO)(Me)(SO4)(P(p-tolyl)3)2, and Facile Elimination of Hard Ligands

T2 - Crystal and Molecular Structures of Ir(CO)(Me)(SO4)(P(p-tolyl)3)2 and [Ir(CO)3(P(p-tolyl)3)2][HSO4]

AU - Randall, Sherri L.

AU - Miller, Cynthia A.

AU - See, Ronald F.

AU - Churchill, Melvyn Rowen

AU - Janik, Thomas S.

AU - Lake, Charles H.

AU - Atwood, Jim D.

PY - 1994/12/1

Y1 - 1994/12/1

N2 - Carbonylation of several iridium(I) complexes, trans-Ir(CO)(R)(P(p-tolyl)3)2 lead to products Ir(CO)2(CO)R)(P(p-tolyl)3)2, R = Me, OCH2Ph; and Ir2(CO)6(P(p-tolyl)3)2, R = OH, OMe, and OC6H4Me) that depend on the nature of the R group. Carbonylation of the iridium(III) complex, Ir(CO)(Me)(SO4)(P(p-tolyl)3)2 leads to two iridium products, [Ir(CO)3(P(p-tolyl)3)2+] and Ir(CO)3(C(O)Me)(P(p-tolyl)3)2 by two different pathways. Structures of Ir(CO)(Me)(SO4)- (P(p-tolyl)3)2 and [Ir(CO)3(P(p-tolyl)3)2][HSO4] were determined to assist in the interpretation. The complex Ir(CO)(Me)(SO4)(P(p-tolyl)3)2 crystallizes in the orthorhombic space group Pbcn with a = 18.237(3), b = 12.572(2), c = 18.584(2) Å, V = 4260.9(11) Å3 and Z = 4. The structure was refined to R = 1.98% for 1640 reflections with F > 6σ(F). The molecule lies on a site of C2 symmetry, necessitating a disorder of carbonyl and methyl ligands. Bond distances around the octahedral iridium(III) center include Ir-CO = 1.823(13), Ir-CH3 = 2.127(14), Ir-–P= 2.398(1) and Ir–O(SO4) = 2.119(4) Å. The species [Ir(CO)3(P(p-tolyl)3)2][HSO4] crystallizes in the monoclinic space group P21/n with a = 11.490(2), b = 12.255(3), c = 30.873(7) Å, β = 92.826(17)°, V = 4342.0(15) Å3 and Z = 4. The structure was refined to R = 6.09% for 2591 reflections with F > 6σ(F). The Ir(CO)3P2 core of the cation has a geometry slightly distorted from D3h symmetry, with Ir–P = 2.363(5) and 2.374(5) Å and Ir-CO = 1.921(21)− 2.012(28) Å. The HSO4− anion undergoes substantial librational motion (or is disordered) and is associated with S–O distances ranging from 1.31(4) through 1.49(3) Å.

AB - Carbonylation of several iridium(I) complexes, trans-Ir(CO)(R)(P(p-tolyl)3)2 lead to products Ir(CO)2(CO)R)(P(p-tolyl)3)2, R = Me, OCH2Ph; and Ir2(CO)6(P(p-tolyl)3)2, R = OH, OMe, and OC6H4Me) that depend on the nature of the R group. Carbonylation of the iridium(III) complex, Ir(CO)(Me)(SO4)(P(p-tolyl)3)2 leads to two iridium products, [Ir(CO)3(P(p-tolyl)3)2+] and Ir(CO)3(C(O)Me)(P(p-tolyl)3)2 by two different pathways. Structures of Ir(CO)(Me)(SO4)- (P(p-tolyl)3)2 and [Ir(CO)3(P(p-tolyl)3)2][HSO4] were determined to assist in the interpretation. The complex Ir(CO)(Me)(SO4)(P(p-tolyl)3)2 crystallizes in the orthorhombic space group Pbcn with a = 18.237(3), b = 12.572(2), c = 18.584(2) Å, V = 4260.9(11) Å3 and Z = 4. The structure was refined to R = 1.98% for 1640 reflections with F > 6σ(F). The molecule lies on a site of C2 symmetry, necessitating a disorder of carbonyl and methyl ligands. Bond distances around the octahedral iridium(III) center include Ir-CO = 1.823(13), Ir-CH3 = 2.127(14), Ir-–P= 2.398(1) and Ir–O(SO4) = 2.119(4) Å. The species [Ir(CO)3(P(p-tolyl)3)2][HSO4] crystallizes in the monoclinic space group P21/n with a = 11.490(2), b = 12.255(3), c = 30.873(7) Å, β = 92.826(17)°, V = 4342.0(15) Å3 and Z = 4. The structure was refined to R = 6.09% for 2591 reflections with F > 6σ(F). The Ir(CO)3P2 core of the cation has a geometry slightly distorted from D3h symmetry, with Ir–P = 2.363(5) and 2.374(5) Å and Ir-CO = 1.921(21)− 2.012(28) Å. The HSO4− anion undergoes substantial librational motion (or is disordered) and is associated with S–O distances ranging from 1.31(4) through 1.49(3) Å.

UR - https://www.scopus.com/pages/publications/0000045216

U2 - 10.1021/om00024a060

DO - 10.1021/om00024a060

M3 - Article

AN - SCOPUS:0000045216

SN - 0276-7333

VL - 13

SP - 5088

EP - 5095

JO - Organometallics

JF - Organometallics

IS - 12

ER -

Randall SL, Miller CA, See RF, Churchill MR, Janik TS, Lake CH et al. Carbonylation of Iridium(I) and Iridium(III) Complexes, trans-Ir(CO)(R)(P(p-tolyl)₃)₂ (R = Me, OMe, OCH₂Ph, OC₆H₄Me, OH) and Ir(CO)(Me)(SO₄)(P(p-tolyl)₃)₂, and Facile Elimination of Hard Ligands: Crystal and Molecular Structures of Ir(CO)(Me)(SO₄)(P(p-tolyl)₃)₂ and [Ir(CO)₃(P(p-tolyl)₃)₂][HSO₄]. Organometallics. 1994 Dec 1;13(12):5088-5095. doi: 10.1021/om00024a060

Carbonylation of Iridium(I) and Iridium(III) Complexes, trans-Ir(CO)(R)(P(p-tolyl)3)2 (R = Me, OMe, OCH2Ph, OC6H4Me, OH) and Ir(CO)(Me)(SO4)(P(p-tolyl)3)2, and Facile Elimination of Hard Ligands: Crystal and Molecular Structures of Ir(CO)(Me)(SO4)(P(p-tolyl)3)2 and [Ir(CO)3(P(p-tolyl)3)2][HSO4]

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