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)

Patrick Achord; Etsuko Fujita; James Muckerman; Brian Scott; George C. Fortman; Manuel Temprado; Xiaochen Cai; Burjor Captain; Derek Isrow; John J. Weir; James Eric McDonough; Carl D. Hoff

doi:10.1021/ic900764e

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)

Patrick Achord, Etsuko Fujita, James Muckerman, Brian Scott, George C. Fortman, Manuel Temprado, Xiaochen Cai, Burjor Captain, Derek Isrow, John J. Weir, James Eric McDonough, Carl D. Hoff

Brookhaven National Laboratory

Research output: Contribution to journal › Article

11 Citations (Scopus)

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 V_CN- 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	https://doi.org/10.1021/ic900764e
Publication status	Published - Aug 17 2009

ASJC Scopus subject areas

Inorganic Chemistry
Physical and Theoretical Chemistry

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Achord, P., Fujita, E., Muckerman, J., Scott, B., Fortman, G. C., Temprado, M., Cai, X., Captain, B., Isrow, D., Weir, J. J., McDonough, J. E., & Hoff, C. D. (2009). 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). Inorganic Chemistry, 48(16), 7891-7904. https://doi.org/10.1021/ic900764e

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

Achord, P, Fujita, E , Muckerman, J, Scott, B, Fortman, GC, Temprado, M, Cai, X, Captain, B, Isrow, D, Weir, JJ, McDonough, JE & Hoff, CD 2009, '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)', Inorganic Chemistry, vol. 48, no. 16, pp. 7891-7904. https://doi.org/10.1021/ic900764e

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. / 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). In: Inorganic Chemistry. 2009 ; Vol. 48, No. 16. pp. 7891-7904.

@article{d3787af54a7c46ae812e6f06a54a61c6,

title = "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)",

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.",

author = "Patrick Achord and Etsuko Fujita and James Muckerman and Brian Scott and Fortman, {George C.} and Manuel Temprado and Xiaochen Cai and Burjor Captain and Derek Isrow and Weir, {John J.} and McDonough, {James Eric} and Hoff, {Carl D.}",

year = "2009",

month = aug,

day = "17",

doi = "10.1021/ic900764e",

language = "English",

volume = "48",

pages = "7891--7904",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "16",

}

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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JF - Inorganic Chemistry

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