Abstract
The enthalpies of binding of a number of N-donor ligands to the complex Mo(PiPr3)2(CO)3 in toluene have been determined by solution calorimetry and equilibrium measurements. The measured binding enthalpies span a range of ∼10 kcal mol-1: δH binding = -8.8±1.2 (N2-Mo(PiPr 3)2(CO)3); -10.3 ±0.8 (N2); -11.2 ±0.4 (AdN3 (Ad = 1 -adamantyl)); -13.8± 0.5 (N2CHSiMe3); -14.9 ± 0.9 (pyrazine=pz); -14.8 ± 0.6 (2,6-Me2pz); -15.5 ± 1.8 (Me2NCN); -16.6 ± 0.4 (CH3CN); -17.0 ± 0.4 (pyridine); -17.5 ± 0.8 ([4-CH3pz][PF6] (in tetrahydrofuran)); -17.6 ± 0.4 (C6H5CN); -18.6 ± 1.8 (N 2CHC (=O)OEt); and -19.3 ± 2.5 kcal moP-1 (pz)Mo(PiPr3)2(CO)3). The value for the isonitrile AdNC (-29.0 ± 0.3) is 12.3 kcal mol-1 more exothermic than that of the nitrile AdCN (- 16.7 ± 0.6 kcal mol -1). The enthalpies of binding of a range of arene nitrile ligands were also studied, and remarkably, most nitrile complexes were clustered within a 1 kcal mol-1 range despite dramatic color changes and variation of VCN- Computed structural and spectroscopic parameters for the complexes Mo (PiPr3)2(CO)3L are in good agreement with experimental data. Computed binding enthalpies for Mo(P iPr3)2(CO)3L exhibit considerable scatter and are generally smaller compared to the experimental values, but relative agreement is reasonable. Computed enthalpies of binding using a larger basis set for Mo(PMe3)2(CO)3L show a better fit to experimental data than that for Mo(PiPr3) 2(CO)3L using a smaller basis set. Crystal structures of Mo(PiPr3)2(CO)3(AdCN), W(P iPr3)2(CO)3(Me2NCN), W (PiPr3)2(CO)3(2,6-F 2C6H3CN), W(PiPr3) 2(CO)3(2,4,6-Me3C6H2CN), W(PiPr3)2(CO)3(2,6-Me 2pz), W(P'Pr3)2(CO)3(AdCN), Mo(PiPr3)2(CO)3(AdNC), and W(P iPr3)2(CO)3(AdNC) are reported.
| Original language | English |
|---|---|
| Pages (from-to) | 7891-7904 |
| Number of pages | 14 |
| Journal | Inorganic Chemistry |
| Volume | 48 |
| Issue number | 16 |
| DOIs | |
| Publication status | Published - Aug 17 2009 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Physical and Theoretical Chemistry
Cite this
Experimental and computational studies of binding of dinitrogen, nitriles, azides, diazoalkanes, pyridine, and pyrazines to M(PR3) 2(CO)3 (M = Mo, W.; R = Me, Pr). / Achord, Patrick; Fujita, Etsuko; Muckerman, James; Scott, Brian; Fortman, George C.; Temprado, Manuel; Cai, Xiaochen; Captain, Burjor; Isrow, Derek; Weir, John J.; McDonough, James Eric; Hoff, Carl D.
In: Inorganic Chemistry, Vol. 48, No. 16, 17.08.2009, p. 7891-7904.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Experimental and computational studies of binding of dinitrogen, nitriles, azides, diazoalkanes, pyridine, and pyrazines to M(PR3) 2(CO)3 (M = Mo, W.; R = Me, Pr)
AU - Achord, Patrick
AU - Fujita, Etsuko
AU - Muckerman, James
AU - Scott, Brian
AU - Fortman, George C.
AU - Temprado, Manuel
AU - Cai, Xiaochen
AU - Captain, Burjor
AU - Isrow, Derek
AU - Weir, John J.
AU - McDonough, James Eric
AU - Hoff, Carl D.
PY - 2009/8/17
Y1 - 2009/8/17
N2 - The enthalpies of binding of a number of N-donor ligands to the complex Mo(PiPr3)2(CO)3 in toluene have been determined by solution calorimetry and equilibrium measurements. The measured binding enthalpies span a range of ∼10 kcal mol-1: δH binding = -8.8±1.2 (N2-Mo(PiPr 3)2(CO)3); -10.3 ±0.8 (N2); -11.2 ±0.4 (AdN3 (Ad = 1 -adamantyl)); -13.8± 0.5 (N2CHSiMe3); -14.9 ± 0.9 (pyrazine=pz); -14.8 ± 0.6 (2,6-Me2pz); -15.5 ± 1.8 (Me2NCN); -16.6 ± 0.4 (CH3CN); -17.0 ± 0.4 (pyridine); -17.5 ± 0.8 ([4-CH3pz][PF6] (in tetrahydrofuran)); -17.6 ± 0.4 (C6H5CN); -18.6 ± 1.8 (N 2CHC (=O)OEt); and -19.3 ± 2.5 kcal moP-1 (pz)Mo(PiPr3)2(CO)3). The value for the isonitrile AdNC (-29.0 ± 0.3) is 12.3 kcal mol-1 more exothermic than that of the nitrile AdCN (- 16.7 ± 0.6 kcal mol -1). The enthalpies of binding of a range of arene nitrile ligands were also studied, and remarkably, most nitrile complexes were clustered within a 1 kcal mol-1 range despite dramatic color changes and variation of VCN- Computed structural and spectroscopic parameters for the complexes Mo (PiPr3)2(CO)3L are in good agreement with experimental data. Computed binding enthalpies for Mo(P iPr3)2(CO)3L exhibit considerable scatter and are generally smaller compared to the experimental values, but relative agreement is reasonable. Computed enthalpies of binding using a larger basis set for Mo(PMe3)2(CO)3L show a better fit to experimental data than that for Mo(PiPr3) 2(CO)3L using a smaller basis set. Crystal structures of Mo(PiPr3)2(CO)3(AdCN), W(P iPr3)2(CO)3(Me2NCN), W (PiPr3)2(CO)3(2,6-F 2C6H3CN), W(PiPr3) 2(CO)3(2,4,6-Me3C6H2CN), W(PiPr3)2(CO)3(2,6-Me 2pz), W(P'Pr3)2(CO)3(AdCN), Mo(PiPr3)2(CO)3(AdNC), and W(P iPr3)2(CO)3(AdNC) are reported.
AB - The enthalpies of binding of a number of N-donor ligands to the complex Mo(PiPr3)2(CO)3 in toluene have been determined by solution calorimetry and equilibrium measurements. The measured binding enthalpies span a range of ∼10 kcal mol-1: δH binding = -8.8±1.2 (N2-Mo(PiPr 3)2(CO)3); -10.3 ±0.8 (N2); -11.2 ±0.4 (AdN3 (Ad = 1 -adamantyl)); -13.8± 0.5 (N2CHSiMe3); -14.9 ± 0.9 (pyrazine=pz); -14.8 ± 0.6 (2,6-Me2pz); -15.5 ± 1.8 (Me2NCN); -16.6 ± 0.4 (CH3CN); -17.0 ± 0.4 (pyridine); -17.5 ± 0.8 ([4-CH3pz][PF6] (in tetrahydrofuran)); -17.6 ± 0.4 (C6H5CN); -18.6 ± 1.8 (N 2CHC (=O)OEt); and -19.3 ± 2.5 kcal moP-1 (pz)Mo(PiPr3)2(CO)3). The value for the isonitrile AdNC (-29.0 ± 0.3) is 12.3 kcal mol-1 more exothermic than that of the nitrile AdCN (- 16.7 ± 0.6 kcal mol -1). The enthalpies of binding of a range of arene nitrile ligands were also studied, and remarkably, most nitrile complexes were clustered within a 1 kcal mol-1 range despite dramatic color changes and variation of VCN- Computed structural and spectroscopic parameters for the complexes Mo (PiPr3)2(CO)3L are in good agreement with experimental data. Computed binding enthalpies for Mo(P iPr3)2(CO)3L exhibit considerable scatter and are generally smaller compared to the experimental values, but relative agreement is reasonable. Computed enthalpies of binding using a larger basis set for Mo(PMe3)2(CO)3L show a better fit to experimental data than that for Mo(PiPr3) 2(CO)3L using a smaller basis set. Crystal structures of Mo(PiPr3)2(CO)3(AdCN), W(P iPr3)2(CO)3(Me2NCN), W (PiPr3)2(CO)3(2,6-F 2C6H3CN), W(PiPr3) 2(CO)3(2,4,6-Me3C6H2CN), W(PiPr3)2(CO)3(2,6-Me 2pz), W(P'Pr3)2(CO)3(AdCN), Mo(PiPr3)2(CO)3(AdNC), and W(P iPr3)2(CO)3(AdNC) are reported.
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U2 - 10.1021/ic900764e
DO - 10.1021/ic900764e
M3 - Article
VL - 48
SP - 7891
EP - 7904
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 16
ER -