A Bent vs. Linear Nitrosyl Paradox. Infrared and X-Ray Photoelectron Spectra of CoCl2(NO)L2 and Crystal Structure with L = P(CH3XC6H5)2

Carolyn Pratt Brock; James P. Collman; Giuliano Dolcetti; Paul H. Farnham; James A. Ibers; J. E. Lester; C. A. Reed

doi:10.1021/ic50124a018

A Bent vs. Linear Nitrosyl Paradox. Infrared and X-Ray Photoelectron Spectra of CoCl₂(NO)L₂ and Crystal Structure with L = P(CH₃XC₆H₅)₂

Carolyn Pratt Brock, James P. Collman^*, Giuliano Dolcetti, Paul H. Farnham, James A. Ibers, J. E. Lester, C. A. Reed

^*Corresponding author for this work

Chemistry

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Abstract

Infrared, pmr, and X-ray photoelectron spectral data are presented to substantiate the existence of conformational isomers of the nitrosyl complexes CoCl₂(NO)L₂. The first isomer A has trigonal-bipyramidal geometry with a linear nitrosyl (NO⁺) while the second isomer B is believed to have square-pyramidal geometry with a bent nitrosyl (NO⁺) at the apex. A low-temperature crystalline form of CoCl₂(NO)(P(CH₃)(C₆H₅)₂)₂ containing almost solely isomer A was found to transform partially to B by grinding in preparation for a Nujol mull. Nitrogen Is electron binding energies suggest an unexpectedly high preference for isomer B at the surface of most solid samples. The crystal and molecular structures of the room-temperature form of CoCl₂(NO)(P(CH₃)(C₆H₅)₂)₂ have been determined from three-dimensional X-ray data collected at room temperature by counter methods. The material crystallizes with 8 molecules in space group C₂h⁶-C2/c of the monoclinic system in a cell of dimensions a= 16.970 (14), b = 17.035 (9), c= 18.735 (8) Å, and ²= 108.00 (2)°. The calculated and observed densities are 1.445 and 1.44(2) g cm^-3, respectively. The structure has been solved and refined by conventional mean. The final R factor (on F) for the 2428 unique reflections having Fo²> 3σ(Fo²) is 0.046. The resultant structure is of isomer A, a somewhat distorted trigonal bipyramid, and there is no evidence for the coexistence of isomer B in the crystal used in the X-ray analysis.

Original language	English (US)
Pages (from-to)	1304-1313
Number of pages	10
Journal	Inorganic chemistry
Volume	12
Issue number	6
DOIs	https://doi.org/10.1021/ic50124a018
State	Published - Jun 1 1973

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Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{4d0e806850eb4db6ac6f560b0ee0c73a,

title = "A Bent vs. Linear Nitrosyl Paradox. Infrared and X-Ray Photoelectron Spectra of CoCl2(NO)L2 and Crystal Structure with L = P(CH3XC6H5)2",

abstract = "Infrared, pmr, and X-ray photoelectron spectral data are presented to substantiate the existence of conformational isomers of the nitrosyl complexes CoCl2(NO)L2. The first isomer A has trigonal-bipyramidal geometry with a linear nitrosyl (NO+) while the second isomer B is believed to have square-pyramidal geometry with a bent nitrosyl (NO+) at the apex. A low-temperature crystalline form of CoCl2(NO)(P(CH3)(C6H5)2)2 containing almost solely isomer A was found to transform partially to B by grinding in preparation for a Nujol mull. Nitrogen Is electron binding energies suggest an unexpectedly high preference for isomer B at the surface of most solid samples. The crystal and molecular structures of the room-temperature form of CoCl2(NO)(P(CH3)(C6H5)2)2 have been determined from three-dimensional X-ray data collected at room temperature by counter methods. The material crystallizes with 8 molecules in space group C2h6-C2/c of the monoclinic system in a cell of dimensions a= 16.970 (14), b = 17.035 (9), c= 18.735 (8) {\AA}, and ²= 108.00 (2)°. The calculated and observed densities are 1.445 and 1.44(2) g cm-3, respectively. The structure has been solved and refined by conventional mean. The final R factor (on F) for the 2428 unique reflections having Fo2> 3σ(Fo2) is 0.046. The resultant structure is of isomer A, a somewhat distorted trigonal bipyramid, and there is no evidence for the coexistence of isomer B in the crystal used in the X-ray analysis.",

author = "Brock, {Carolyn Pratt} and Collman, {James P.} and Giuliano Dolcetti and Farnham, {Paul H.} and Ibers, {James A.} and Lester, {J. E.} and Reed, {C. A.}",

year = "1973",

month = jun,

day = "1",

doi = "10.1021/ic50124a018",

language = "English (US)",

volume = "12",

pages = "1304--1313",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "6",

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TY - JOUR

T1 - A Bent vs. Linear Nitrosyl Paradox. Infrared and X-Ray Photoelectron Spectra of CoCl2(NO)L2 and Crystal Structure with L = P(CH3XC6H5)2

AU - Brock, Carolyn Pratt

AU - Collman, James P.

AU - Dolcetti, Giuliano

AU - Farnham, Paul H.

AU - Ibers, James A.

AU - Lester, J. E.

AU - Reed, C. A.

PY - 1973/6/1

Y1 - 1973/6/1

N2 - Infrared, pmr, and X-ray photoelectron spectral data are presented to substantiate the existence of conformational isomers of the nitrosyl complexes CoCl2(NO)L2. The first isomer A has trigonal-bipyramidal geometry with a linear nitrosyl (NO+) while the second isomer B is believed to have square-pyramidal geometry with a bent nitrosyl (NO+) at the apex. A low-temperature crystalline form of CoCl2(NO)(P(CH3)(C6H5)2)2 containing almost solely isomer A was found to transform partially to B by grinding in preparation for a Nujol mull. Nitrogen Is electron binding energies suggest an unexpectedly high preference for isomer B at the surface of most solid samples. The crystal and molecular structures of the room-temperature form of CoCl2(NO)(P(CH3)(C6H5)2)2 have been determined from three-dimensional X-ray data collected at room temperature by counter methods. The material crystallizes with 8 molecules in space group C2h6-C2/c of the monoclinic system in a cell of dimensions a= 16.970 (14), b = 17.035 (9), c= 18.735 (8) Å, and ²= 108.00 (2)°. The calculated and observed densities are 1.445 and 1.44(2) g cm-3, respectively. The structure has been solved and refined by conventional mean. The final R factor (on F) for the 2428 unique reflections having Fo2> 3σ(Fo2) is 0.046. The resultant structure is of isomer A, a somewhat distorted trigonal bipyramid, and there is no evidence for the coexistence of isomer B in the crystal used in the X-ray analysis.

AB - Infrared, pmr, and X-ray photoelectron spectral data are presented to substantiate the existence of conformational isomers of the nitrosyl complexes CoCl2(NO)L2. The first isomer A has trigonal-bipyramidal geometry with a linear nitrosyl (NO+) while the second isomer B is believed to have square-pyramidal geometry with a bent nitrosyl (NO+) at the apex. A low-temperature crystalline form of CoCl2(NO)(P(CH3)(C6H5)2)2 containing almost solely isomer A was found to transform partially to B by grinding in preparation for a Nujol mull. Nitrogen Is electron binding energies suggest an unexpectedly high preference for isomer B at the surface of most solid samples. The crystal and molecular structures of the room-temperature form of CoCl2(NO)(P(CH3)(C6H5)2)2 have been determined from three-dimensional X-ray data collected at room temperature by counter methods. The material crystallizes with 8 molecules in space group C2h6-C2/c of the monoclinic system in a cell of dimensions a= 16.970 (14), b = 17.035 (9), c= 18.735 (8) Å, and ²= 108.00 (2)°. The calculated and observed densities are 1.445 and 1.44(2) g cm-3, respectively. The structure has been solved and refined by conventional mean. The final R factor (on F) for the 2428 unique reflections having Fo2> 3σ(Fo2) is 0.046. The resultant structure is of isomer A, a somewhat distorted trigonal bipyramid, and there is no evidence for the coexistence of isomer B in the crystal used in the X-ray analysis.

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DO - 10.1021/ic50124a018

M3 - Article

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SN - 0020-1669

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JO - Inorganic chemistry

JF - Inorganic chemistry

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A Bent vs. Linear Nitrosyl Paradox. Infrared and X-Ray Photoelectron Spectra of CoCl₂(NO)L₂ and Crystal Structure with L = P(CH₃XC₆H₅)₂

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