Carbon-oxygen bond formation on rhodium centers. Synthesis, characterization, crystal structure, and reactions of trans-phorh(co)(pph3)2

Karen A. Bernard; Melvyn Rowen Churchill; Thomas S. Janik; Jim D. Atwood

doi:10.1021/om00115a003

Carbon-oxygen bond formation on rhodium centers. Synthesis, characterization, crystal structure, and reactions of trans-phorh(co)(pph₃)₂

Karen A. Bernard
, Melvyn Rowen Churchill
, Thomas S. Janik
, Jim D. Atwood

Chemistry

SUNY Buffalo
State University of New York System

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

24 Scopus citations

Abstract

The synthesis of a rhodium phenoxide is reported. The complex trans-PhORh(CO)(PPh₃)₂ crystallizes in the centrosymmetric monoclinic space group P2_l/c with a = 15.794 (3) Å, b = 11.449 (2) Å, c = 20.025 (3) Å, β = 100.220 (13)°, V = 3562 (1) Å³, and Z = 4. Diffraction data (Mo Kα, 2θ = 4.5-50.0°) were collected with a Syntex P2₁ diffractometer, and the structure was refined to R_F = 2.8% for 5293 reflections. The structure is isomorphous with the iridium analogue. Important dimensions include Rh‒P = 2.337 (l)-2.357 (1) Å, Rh-CO = 1.801 (3) Å, Rh-OPh = 2.044 (2) Å, and Rh-O-C(phenoxide) = 125.52 (19)°. This complex reacts with Ph₂CHC(O)Cl to give the ester Ph₂CHC(O)OPh and with MeI to give anisole, PhOMe. The formation of anisole from the rhodium phenoxide is in contrast to the failure to eliminate ethers from similar iridium complexes and is consistent with the known preference for elimination from second-row (rather than third-row) transition-metal complexes.

Original language	English
Pages (from-to)	12-16
Number of pages	5
Journal	Organometallics
Volume	9
Issue number	1
DOIs	https://doi.org/10.1021/om00115a003
State	Published - 1990

Access to Document

10.1021/om00115a003

Cite this

@article{c871f5fabdca45b88e7fdb2d4b9aca11,

title = "Carbon-oxygen bond formation on rhodium centers. Synthesis, characterization, crystal structure, and reactions of trans-phorh(co)(pph3)2",

abstract = "The synthesis of a rhodium phenoxide is reported. The complex trans-PhORh(CO)(PPh3)2 crystallizes in the centrosymmetric monoclinic space group P2l/c with a = 15.794 (3) {\AA}, b = 11.449 (2) {\AA}, c = 20.025 (3) {\AA}, β = 100.220 (13)°, V = 3562 (1) {\AA}3, and Z = 4. Diffraction data (Mo Kα, 2θ = 4.5-50.0°) were collected with a Syntex P21 diffractometer, and the structure was refined to RF = 2.8\% for 5293 reflections. The structure is isomorphous with the iridium analogue. Important dimensions include Rh‒P = 2.337 (l)-2.357 (1) {\AA}, Rh-CO = 1.801 (3) {\AA}, Rh-OPh = 2.044 (2) {\AA}, and Rh-O-C(phenoxide) = 125.52 (19)°. This complex reacts with Ph2CHC(O)Cl to give the ester Ph2CHC(O)OPh and with MeI to give anisole, PhOMe. The formation of anisole from the rhodium phenoxide is in contrast to the failure to eliminate ethers from similar iridium complexes and is consistent with the known preference for elimination from second-row (rather than third-row) transition-metal complexes.",

author = "Bernard, \{Karen A.\} and Churchill, \{Melvyn Rowen\} and Janik, \{Thomas S.\} and Atwood, \{Jim D.\}",

year = "1990",

doi = "10.1021/om00115a003",

language = "English",

volume = "9",

pages = "12--16",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "1",

}

TY - JOUR

T1 - Carbon-oxygen bond formation on rhodium centers. Synthesis, characterization, crystal structure, and reactions of trans-phorh(co)(pph3)2

AU - Bernard, Karen A.

AU - Churchill, Melvyn Rowen

AU - Janik, Thomas S.

AU - Atwood, Jim D.

PY - 1990

Y1 - 1990

N2 - The synthesis of a rhodium phenoxide is reported. The complex trans-PhORh(CO)(PPh3)2 crystallizes in the centrosymmetric monoclinic space group P2l/c with a = 15.794 (3) Å, b = 11.449 (2) Å, c = 20.025 (3) Å, β = 100.220 (13)°, V = 3562 (1) Å3, and Z = 4. Diffraction data (Mo Kα, 2θ = 4.5-50.0°) were collected with a Syntex P21 diffractometer, and the structure was refined to RF = 2.8% for 5293 reflections. The structure is isomorphous with the iridium analogue. Important dimensions include Rh‒P = 2.337 (l)-2.357 (1) Å, Rh-CO = 1.801 (3) Å, Rh-OPh = 2.044 (2) Å, and Rh-O-C(phenoxide) = 125.52 (19)°. This complex reacts with Ph2CHC(O)Cl to give the ester Ph2CHC(O)OPh and with MeI to give anisole, PhOMe. The formation of anisole from the rhodium phenoxide is in contrast to the failure to eliminate ethers from similar iridium complexes and is consistent with the known preference for elimination from second-row (rather than third-row) transition-metal complexes.

AB - The synthesis of a rhodium phenoxide is reported. The complex trans-PhORh(CO)(PPh3)2 crystallizes in the centrosymmetric monoclinic space group P2l/c with a = 15.794 (3) Å, b = 11.449 (2) Å, c = 20.025 (3) Å, β = 100.220 (13)°, V = 3562 (1) Å3, and Z = 4. Diffraction data (Mo Kα, 2θ = 4.5-50.0°) were collected with a Syntex P21 diffractometer, and the structure was refined to RF = 2.8% for 5293 reflections. The structure is isomorphous with the iridium analogue. Important dimensions include Rh‒P = 2.337 (l)-2.357 (1) Å, Rh-CO = 1.801 (3) Å, Rh-OPh = 2.044 (2) Å, and Rh-O-C(phenoxide) = 125.52 (19)°. This complex reacts with Ph2CHC(O)Cl to give the ester Ph2CHC(O)OPh and with MeI to give anisole, PhOMe. The formation of anisole from the rhodium phenoxide is in contrast to the failure to eliminate ethers from similar iridium complexes and is consistent with the known preference for elimination from second-row (rather than third-row) transition-metal complexes.

UR - https://www.scopus.com/pages/publications/0025210724

U2 - 10.1021/om00115a003

DO - 10.1021/om00115a003

M3 - Article

AN - SCOPUS:0025210724

SN - 0276-7333

VL - 9

SP - 12

EP - 16

JO - Organometallics

JF - Organometallics

IS - 1

ER -

Carbon-oxygen bond formation on rhodium centers. Synthesis, characterization, crystal structure, and reactions of trans-phorh(co)(pph₃)₂

Abstract

Access to Document

Other files and links

Fingerprint

Cite this