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Single-crystal X-ray and neutron diffraction studies of an. eta. sup 2 -dihydrogen transition-metal complex: trans-(Fe(. eta. sup 2 -H sub 2 )(H)(PPh sub 2 CH sub 2 CH sub 2 PPh sub 2 ) sub 2 )BPh sub 4

Journal Article · · Journal of the American Chemical Society; (USA)
DOI:https://doi.org/10.1021/ja00206a009· OSTI ID:6973450
 [1];  [2]; ; ; ;  [3]
  1. Univ. of Southern Maine, Portland (USA) Brookhaven National Lab., Upton, NY (USA)
  2. Brookhaven National Lab., Upton, NY (USA)
  3. Univ. of Toronto, Ontario (Canada)
+ Show Author Affiliations
The H-H distance in the {eta}{sup 2}H{sub 2} ligand in (Fe({eta}{sup 2}-H{sub 2})H(dppe){sub 2})BPh{sub 4}, 1 BPh{sub 4}, dppe = PPh{sub 2}CH{sub 2}CH{sub 2}PPh{sub 2}, is 0.816 (16) {angstrom} as determined by neutron diffraction on a crystal of volume 2.62 mm{sup 3} at 20 K: 1-BPh{sub 4} is monoclinic, space group C2/c, a = 16.999 (7) {angstrom}, b = 16.171 (2) {angstrom}, c = 22.114 (5) {angstrom}, {beta} = 102.52 (2){degree}, U = 5,934.4 (2) {angstrom}{sup 3}, and D{sub c} = 1.315 g cm{sup {minus}3} for Z = 4; R(F) = 0.071, R(F{sup 2}) = 0.110, R{sub w}(F{sup 2}) = 0.113 for 4,116 reflections with I {>=} 3{sigma}(I). The H-H separation is 0.87 (3) {angstrom} as determined by X-ray diffraction at 298 K: monoclinic, C2/c, a = 17.327 (3) {angstrom}, b = 16.407 (4) {angstrom}, c = 22.224 (3) {angstrom}, {beta} = 102.87 (1){degree}, U = 6,159.2 (1) {angstrom}{sup 3}, and D{sub c} = 1.267 g cm{sup {minus}3} for Z = 4; R(F) = 0.038, R{sub w}(F) = 0.034, for 3,673 reflections (I {>=} 3{sigma}(I)). These {eta}{sup 2}-H{sub 2} distances agree with the X-ray value of 0.89 (11) {angstrom} reported for the tetrafluoroborate salt, 1-BF{sub 4}. As was found for 1-BF{sub 4}, 1-BPh{sub 4} contains an {eta}{sup 2}-H{sub 2} ligand that is symmetrically side-on bonded to the iron and trans to the terminal hydride such that the Fe has a distorted octahedral configuration. These diffraction studies serve to calibrate H-H distances obtained by the T{sub 1} NMR method for dihydrogen complexes in solution where the H{sub 2} ligand is suggested to be rapidly spinning. The H-H distance is the same as that in W({eta}{sup 2}-H{sub 2})(CO){sub 3}(P(i-Pr){sub 3}){sub 2} despite the fact that the tungsten complex has a more labile H{sub 2} ligand. The terminal hydride-iron distance of 1.535 (12) {angstrom} as determined by neutron diffraction is shorter than the distances to the dihydrogen ligand (H-Fe = 1.616 (10) {angstrom}).
DOE Contract Number:
AC02-76CH00016
OSTI ID:
6973450
Journal Information:
Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:24; ISSN 0002-7863; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

36 MATERIALS SCIENCE
360102* -- Metals & Alloys-- Structure & Phase Studies
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
DIFFRACTION
ELEMENTS
EXPERIMENTAL DATA
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
METALS
NEUTRON DIFFRACTION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
SCATTERING
TRANSITION ELEMENT COMPLEXES