X-ray Crystallographic Study of the Complexes Cr(PCl3)(CO)5, W(PCl3)(CO)5, Cr(PBr3)(CO)5, W(PBr3)(CO)5 and Mo(PMe3)(CO)5: Insight into .pi.-Acceptance by Phosphorus

Davies, Murray S.; Aroney, M. J.; Buys, Irmi E.; Hambley, Trevor W.; Calvert, J. L.

doi:10.1021/ic00105a051

Cited by 45 publications

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“…Similar comparisons between the Mo-P bond distances in 2 and other (L)Mo(CO) 5 complexes indicates there is little correlation between the electronic influence of a phosphine ligand and the metal-phosphorus bond. The Mo-P bond length of 2 is 2.5016(11) Å is again almost identical to the Mo-P bond distance of several (L)Mo(CO) 5 complexes [L = PMe 3 (2.5082 Å ) [11], P(CH 2 CH 2 CN) 3 (2.506 Å ) [14], PPh 2 (CF@CF 2 ) (2.5168 Å )] [7] bearing phosphines with varying electronic characteristics. The equatorial metal carbonyl bonds are also relatively insensitive to the electronic nature of the phosphine ligand.…”

Section: Resultssupporting

confidence: 55%

“…The Cr-P bond distance in 1 of is 2.3663(9) Å and the Mo-P bond length of 2 is 2.5016(11) Å . The Cr-P bond length of (pfepp)Cr(CO) 5 is essentially identical to the Cr-P bond length of 2.3664(5) Å in (PMe 3 )Cr(CO) 5 [11] and is only slightly shorter than the Cr-P bond of 2.422(1) Å in the PPh 3 analog [12,13]. Similar comparisons between the Mo-P bond distances in 2 and other (L)Mo(CO) 5 complexes indicates there is little correlation between the electronic influence of a phosphine ligand and the metal-phosphorus bond.…”

Section: Resultsmentioning

confidence: 61%

“…The equatorial metal carbonyl bonds are also relatively insensitive to the electronic nature of the phosphine ligand. The average M-C eq for (PF 3 )Mo(CO) 5 is 2.045 Å [12] and the average bond length for the (PMe 3 )Mo(CO) 5 analog is 2.036 Å [11]. Similar comparisons for the chromium complexes also show no dependence of the M-C eq bond length with the phosphine ligand.…”

Section: Resultsmentioning

confidence: 67%

“…Similar comparisons for the chromium complexes also show no dependence of the M-C eq bond length with the phosphine ligand. The average M-C eq for (PF 3 )Cr(CO) 5 is 1.886 Å [12] and the bond length for the (PMe 3 )Mo-(CO) 5 analog is 1.850(2) Å [11]. The average M-C eq bond length in the pfepp derivatives is 1.903 Å for 1 and 2.049 Å for 2.…”

Section: Resultsmentioning

confidence: 96%

“…Table 3 shows a list of M-C ax bond distances for a number of (L)Mo(CO) 5 and (L)Cr(CO) 5 complexes. In both series, the longest bond belongs to the PCl 3 derivative (1.900(4) Å for (PCl 3 )Cr(CO) 5 and 2.035(2) Å for (PCl 3 )Mo(CO) 5 ) [11,12] and the shortest bond occurs in the PMe 3 derivative (1.850(2) and 1.984(4) for the Cr and Mo complexes, respectively) [11]. The M-C ax bond length data for 1 and 2 (1.870(4) Å for 1 and 2.012(5) Å for 2) clearly show the electronic influence of the pfepp ligand approximates phosphites and PPh 2 (CF@CF 2 ).…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and characterization of chromium and molybdenum(0) complexes bearing the (pentafluoroethyl)diphenylphosphine (pfepp) ligand

Palcic¹,

Baughman²,

Golynskiy³

et al. 2005

Journal of Organometallic Chemistry

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Section: Resultssupporting

confidence: 55%

Section: Resultsmentioning

confidence: 61%

Section: Resultsmentioning

confidence: 67%

Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 99%

See 3 more Smart Citations

Synthesis and characterization of chromium and molybdenum(0) complexes bearing the (pentafluoroethyl)diphenylphosphine (pfepp) ligand

Palcic¹,

Baughman²,

Golynskiy³

et al. 2005

Journal of Organometallic Chemistry

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Molecular structure and binding energies of monosubstituted hexacarbonyls of chromium, molybdenum, and tungsten: Relativistic density functional study

Wllen

1997

J. Comput. Chem.

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Relativistic density functional calculations have been carried out for the group VI transition metal carbonyls M(CO)5L (M=Cr, Mo, W; L=OH2, NH3, PH3, PMe3, N2, CO, OC (isocarbonyl), CS, CH2, CF2, CCl2, NO+). The optimized molecular structures and M(SINGLE BOND)L bond dissociation energies, as well as the metal–carbonyl bond energy of the trans CO group, have been calculated. Besides the marked dependence of the trans M(SINGLE BOND)CO bond length on the type of ligand L, such an effect on the that bond energy is also observed. For the chromium compounds, the trans Cr(SINGLE BOND)CO bond length varies from 184 to 199 pm and its bond energy from 242 to 150 kJ/mol. For the molybdenum compounds, the range is 197 to 216 pm and 253 to 128 kJ/mol and, for tungsten, 198 to 214 pm and 293 to 159 kJ/mol. The observed trends can be explained with the π acceptor strength of the L ligand. © 1997 John Wiley & Sons, Inc. J Comput Chem 18: 1985–1992, 1997

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Interpretation of ³¹P‐NMR Coordination Shifts for Phosphane Ligands. Ab Initio ECP/DFT Study of Chemical Shift Tensors in M(CO)₅L [M = Cr, Mo, W; L = PH₃, P(CH₃)₃, PF₃, PCl₃]

Kaupp

1996

Chem. Ber.

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The 31P chemical shift tensors of the transition-metal phosphane complexes M(CO)5PX3 (M = Cr, Mo, W; X = H, CH3, F, C1) were studied using a combination of density functional theory and ab initio effective-core potentials. The calculated isotropic shifts agree well with experimental results both for the free ligands and for the complexes, with the largest deviations occuring for the tungsten complexes. A breakdown of the computed phosphorus shielding tensors into contributions from localized molecular orbitals (LMOs) indicates that the positive coordination shift of PH3 and P(CH3)3 is due to increased paramagnetic contributions from the phosphorus Not long ago, Kutzelnigg et al. stated"] that "a qualitative understanding of the rules that govern 31P shifts has so far appeared to be a hopeless task". While a series of ab initio calculations by the Bochum group [',2] and by other^ [^-^] on small to medium-sized phosphorus-containing molecules have improved this situation to some extent, the above statement unfortunately is still valid for the theoretical understanding of "P-NMR chemical shifts in transition-metal complexes [6*7]. This is due to the importance of electron correlation in systems containing transition mctalsl81. Thus, the distributed-gauge-origin variants of the coupled Hartree-Fock (CHF) method, which have been very successful for the calculation and interpretation of NMR chemical shifts in "normal" main-group specie^['^^], are not generally applicable to transition-metal compounds. The large cost in computational resources of recently developed post-CHF methods[l01 (which account for electron correlation) has so far prevented their application to transition-metal complexes.Recently, it has been shown that methods based on density functional theory (DFT) provide an attractive alternative to standard ab inito-correlated approaches to the calculation of NMR chemical Due to the implicit inclusion of electron correlation with comparatively low computational effort, DFT methods are particularly suitable for transition-metal complexes. This also holds for the lone pair (P-M cr bonding) LMO to S,. A similar increase of this contribution is found for PF3 and PC13. However, for PC13 complexes these terms are overcompensated by a reduction in the paramagnetic contributions from the P-C1 bonds and by shielding contributions from metal-centered orbitals. This results in a negative overall coordiantion shift. A partial cancellation is found with P(CH& and with PF3. The changes in the 31P-shift tensors of the same phosphane ligands upon protonation are qualitatively and quantitatively very different from the coordination shifts and do not provide good models for the latter.computation of NMR-chemical shift tensors, as demonstrated by our recent applications of the sum-over-states density-functional perturbation theory (SOS-DFPT) approach["], e.g. to I3C and 1 7 0 shift tensors in carbonyl comp l e x e~[ '~~'~] and clusters [20], to 1 7 0 shifts in 0x0 complexes['6], and to I3C shift tensors for interstitial car...

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X-ray Crystallographic Study of the Complexes Cr(PCl3)(CO)5, W(PCl3)(CO)5, Cr(PBr3)(CO)5, W(PBr3)(CO)5 and Mo(PMe3)(CO)5: Insight into .pi.-Acceptance by Phosphorus

Cited by 45 publications

References 0 publications

Synthesis and characterization of chromium and molybdenum(0) complexes bearing the (pentafluoroethyl)diphenylphosphine (pfepp) ligand

Synthesis and characterization of chromium and molybdenum(0) complexes bearing the (pentafluoroethyl)diphenylphosphine (pfepp) ligand

Molecular structure and binding energies of monosubstituted hexacarbonyls of chromium, molybdenum, and tungsten: Relativistic density functional study

Interpretation of ³¹P‐NMR Coordination Shifts for Phosphane Ligands. Ab Initio ECP/DFT Study of Chemical Shift Tensors in M(CO)₅L [M = Cr, Mo, W; L = PH₃, P(CH₃)₃, PF₃, PCl₃]

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X-ray Crystallographic Study of the Complexes Cr(PCl3)(CO)5, W(PCl3)(CO)5, Cr(PBr3)(CO)5, W(PBr3)(CO)5 and Mo(PMe3)(CO)5: Insight into .pi.-Acceptance by Phosphorus

Cited by 45 publications

References 0 publications

Synthesis and characterization of chromium and molybdenum(0) complexes bearing the (pentafluoroethyl)diphenylphosphine (pfepp) ligand

Synthesis and characterization of chromium and molybdenum(0) complexes bearing the (pentafluoroethyl)diphenylphosphine (pfepp) ligand

Molecular structure and binding energies of monosubstituted hexacarbonyls of chromium, molybdenum, and tungsten: Relativistic density functional study

Interpretation of 31P‐NMR Coordination Shifts for Phosphane Ligands. Ab Initio ECP/DFT Study of Chemical Shift Tensors in M(CO)5L [M = Cr, Mo, W; L = PH3, P(CH3)3, PF3, PCl3]

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Interpretation of ³¹P‐NMR Coordination Shifts for Phosphane Ligands. Ab Initio ECP/DFT Study of Chemical Shift Tensors in M(CO)₅L [M = Cr, Mo, W; L = PH₃, P(CH₃)₃, PF₃, PCl₃]