Can M(H)(2)(H-2)(PXP) pincer complexes (M = Fe, Ru, Os; X = N, O, S) serve as catalyst lead structures for NH3 synthesis from N-2 and H-2?

M. Holscher, Martin H. G. Prechtl, W. Leitner

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

The potential of pincer complexes [M(H)(2)(H-2)(PXP)] (M=Fe, Ru, Os; X=N, O, S) to coordinate, activate, and thus catalyze the reaction of N-2 with classical or nonclassical hydrogen centers present at the metal center, with the aim of forming NH3 with H-2 as the only other reagent, was explored by means of DF (density functional) calculations. Screening of various complexes for their ability to perform initial hydrogen transfer to coordinated N-2 showed ruthenium pincer complexes to be more promising than the corresponding iron and osmium analogues. The ligand backbone influences the reaction dramatically: the presence of pyridine and thioether groups as backbones in the ligand result in inactive and result in unprecedented low activation barriers (23.7 and 22.1 kcal mol(-1), respectively), low enough to be interesting for practical application. Catalytic cycles were calculated for [Ru(H)(2)(H-2)(POP)] catalysts (POP= 2,5-bis(dimethylphosphanylmethyl)furan and 2,6-bis(dimethylphosphanylmethyl)-gamma-pyran). The height of activation barriers for the furan system is somewhat more advantageous. Formation of inactive metal nitrides has not been observed. SCRF calculations were used to introduce solvent (toluene) effects. The Gibbs free energies of activation of the numerous single reaction steps do not change significantly when solvent is included. The reaction steps associated with the formation of the active catalyst from precursors [M(H)(2)(H-2)(PXP)] were also calculated. The otherwise inactive pyridine ligand system allows for the generation of the active catalyst species, whereas the ether ligand systems show activation barriers that could prohibit practical application. Consequently the generation of the active catalyst species needs to be addressed in further studies.
OriginalsprogEngelsk
TidsskriftChemistry: A European Journal
Vol/bind13
Udgave nummer23
Sider (fra-til)6636-6643
Antal sider8
ISSN0947-6539
DOI
StatusUdgivet - 2007
Udgivet eksterntJa

Citer dette

@article{090aa9faef764f97b9cbc7809951f06b,
title = "Can M(H)(2)(H-2)(PXP) pincer complexes (M = Fe, Ru, Os; X = N, O, S) serve as catalyst lead structures for NH3 synthesis from N-2 and H-2?",
abstract = "The potential of pincer complexes [M(H)(2)(H-2)(PXP)] (M=Fe, Ru, Os; X=N, O, S) to coordinate, activate, and thus catalyze the reaction of N-2 with classical or nonclassical hydrogen centers present at the metal center, with the aim of forming NH3 with H-2 as the only other reagent, was explored by means of DF (density functional) calculations. Screening of various complexes for their ability to perform initial hydrogen transfer to coordinated N-2 showed ruthenium pincer complexes to be more promising than the corresponding iron and osmium analogues. The ligand backbone influences the reaction dramatically: the presence of pyridine and thioether groups as backbones in the ligand result in inactive and result in unprecedented low activation barriers (23.7 and 22.1 kcal mol(-1), respectively), low enough to be interesting for practical application. Catalytic cycles were calculated for [Ru(H)(2)(H-2)(POP)] catalysts (POP= 2,5-bis(dimethylphosphanylmethyl)furan and 2,6-bis(dimethylphosphanylmethyl)-gamma-pyran). The height of activation barriers for the furan system is somewhat more advantageous. Formation of inactive metal nitrides has not been observed. SCRF calculations were used to introduce solvent (toluene) effects. The Gibbs free energies of activation of the numerous single reaction steps do not change significantly when solvent is included. The reaction steps associated with the formation of the active catalyst from precursors [M(H)(2)(H-2)(PXP)] were also calculated. The otherwise inactive pyridine ligand system allows for the generation of the active catalyst species, whereas the ether ligand systems show activation barriers that could prohibit practical application. Consequently the generation of the active catalyst species needs to be addressed in further studies.",
keywords = "activation energy ammonia density functional calculations homogeneous catalysis pincer complexes ruthenium molybdenum triamidoamine complexes ruthenium hydride complexes gaussian-basis sets dinitrogen complexes metal-complexes nitrogen-fixation coordinated dinitrogen molecular nitrogen mild conditions atoms li Chemistry",
author = "M. Holscher and Prechtl, {Martin H. G.} and W. Leitner",
note = "ISI Document Delivery No.: 199QQ Times Cited: 12 Cited Reference Count: 55 Cited References: Abdur-Rashid K, 2000, ORGANOMETALLICS, V19, P1652, DOI 10.1021/om990669i ANDRAE D, 1990, THEOR CHIM ACTA, V77, P1203 Aneetha H, 2002, ORGANOMETALLICS, V21, P628, DOI 10.1021/om010730v BECKE AD, 1993, J CHEM PHYS, V98, P5648, DOI 10.1063/1.464913 BOBADOVAPARVANO.Q, 2006, J AM CHEM SOC, V128, P11391 BOBADOVAPARVANO.Q, 2005, ANGEW CHEM, V117, P7263 Bobadova-Parvanova P, 2005, ANGEW CHEM INT EDIT, V44, P7101, DOI 10.1002/anie.200501371 CHATT J, 1978, CHEM REV, V78, P589, DOI 10.1021/cr60316a001 Clentsmith GKB, 1999, J AM CHEM SOC, V121, P10444, DOI 10.1021/ja9921219 Franke O, 2002, Z ANORG ALLG CHEM, V628, P2395, DOI 10.1002/1521-3749(200211)628:11<2395::AID-ZAAC2395>3.0.CO;2-M Frisch M. J., 2004, GAUSSIAN 03 REVISION Fryzuk MD, 2003, CHEM REC, V3, P2, DOI 10.1002/tcr.10044 Fryzuk MD, 1997, SCIENCE, V275, P1445, DOI 10.1126/science.275.5305.1445 Giunta D, 2003, ADV SYNTH CATAL, V345, P1139, DOI 10.1002/adsc.200303091 Gusev DG, 2000, ORGANOMETALLICS, V19, P3429, DOI 10.1021/om0003842 HAGGIN J, 1993, CHEM ENG NEWS, V71, P23, DOI 10.1021/cen-v071n022.p023 HENDERSON RA, 1982, J CHEM SOC DALTON, P917, DOI 10.1039/dt9820000917 HIDAI M, 1999, TOP ORGANOMET CHEM, V3, P227 Himmel H.-J., 2006, ANGEW CHEM, V118, P6412, DOI 10.1002/ange.200502892 Himmel HJ, 2006, ANGEW CHEM INT EDIT, V45, P6264, DOI 10.1002/anie.200502892 Holscher M, 2006, EUR J INORG CHEM, P4407, DOI 10.1002/ejic.200600548 Kozak CM, 2004, ANGEW CHEM INT EDIT, V43, P1186, DOI 10.1002/anie.200301712 KOZAK CM, 2004, ANGEW CHEM, V116, P1206, DOI 10.1002/ange.200301712 LEE CT, 1988, PHYS REV B, V37, P785, DOI 10.1103/PhysRevB.37.785 Le Guennic B, 2005, CHEM-EUR J, V11, P7448, DOI 10.1002/chem.200500935 MacKay BA, 2004, CHEM REV, V104, P385, DOI 10.1021/cr020610c Major Q, 2005, ORGANOMETALLICS, V24, P2492, DOI 10.1021/om050053v Miyachi H, 2005, J PHYS CHEM A, V109, P8800, DOI 10.1021/jp053308r Musaev DG, 2007, INORG CHEM, V46, P2709, DOI 10.1021/ic062405b Ohki Y, 2007, ANGEW CHEM INT EDIT, V46, P3180, DOI 10.1002/anie.200605245 Ohki Y., 2007, ANGEW CHEM, V119, P3242, DOI 10.1002/ange.200605245 Pool JA, 2004, NATURE, V427, P527, DOI 10.1038/nature02274 Prechtl M. H. G., 2007, ANGEW CHEM, V119, P2319, DOI 10.1002/ange.200603677 Prechtl MHG, 2007, CHEM-EUR J, V13, P1539, DOI 10.1002/chem.200600897 Prechtl MHG, 2007, ANGEW CHEM INT EDIT, V46, P2269, DOI 10.1002/anie.200603677 Reiher M, 2005, INORG CHEM, V44, P9640, DOI 10.1021/ic0517568 Ritleng V, 2004, J AM CHEM SOC, V126, P6150, DOI 10.1021/ja0306415 SCHAFER A, 1992, J CHEM PHYS, V97, P2571 SCHAFER A, 1994, J CHEM PHYS, V100, P5829 Schlogl R, 2003, ANGEW CHEM INT EDIT, V42, P2004, DOI 10.1002/anie.200301553 Schlogl R., 2003, ANGEW CHEM, V115, P2050, DOI 10.1002/ange.200301553 Schrock RR, 2005, ACCOUNTS CHEM RES, V38, P955, DOI 10.1021/ar0501121 Schrock RR, 2003, CHEM COMMUN, P2389, DOI 10.1039/b307784p Shaver MP, 2003, ADV SYNTH CATAL, V345, P1061, DOI 10.1002/adsc.200303081 STEPHENS PJ, 1994, J PHYS CHEM-US, V98, P11623, DOI 10.1021/j100096a001 Studt F, 2006, EUR J INORG CHEM, P291, DOI 10.1002/ejic.200500693 Studt F, 2006, J COMPUT CHEM, V27, P1278, DOI 10.1002/jcc.20413 Studt F, 2005, ANGEW CHEM INT EDIT, V44, P5639, DOI 10.1002/anie.200501485 Tomasi J, 2005, CHEM REV, V105, P2999, DOI 10.1021/cr9904009 VOSKO SH, 1980, CAN J PHYS, V58, P1200 Yandulov DV, 2003, INORG CHEM, V42, P796, DOI 10.1021/ic020505l Yandulov DV, 2005, INORG CHEM, V44, P1103, DOI 10.1021/ic040095w Yandulov DV, 2003, SCIENCE, V301, P76, DOI 10.1126/science.1085326 Yandulov DV, 2002, J AM CHEM SOC, V124, P6252, DOI 10.1021/ja020186x Zhang J, 2004, ORGANOMETALLICS, V23, P4026, DOI 10.1021/om049716j Hoelscher, Markus Prechtl, Martin H. G. Leitner, Walter Prechtl, Martin/A-7416-2008 Prechtl, Martin/0000-0003-2155-8006 12 Wiley-v c h verlag gmbh Weinheim",
year = "2007",
doi = "10.1002/chem.200700289",
language = "English",
volume = "13",
pages = "6636--6643",
journal = "Chemistry: A European Journal",
issn = "0947-6539",
publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",
number = "23",

}

Can M(H)(2)(H-2)(PXP) pincer complexes (M = Fe, Ru, Os; X = N, O, S) serve as catalyst lead structures for NH3 synthesis from N-2 and H-2? / Holscher, M.; Prechtl, Martin H. G.; Leitner, W.

I: Chemistry: A European Journal, Bind 13, Nr. 23, 2007, s. 6636-6643.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Can M(H)(2)(H-2)(PXP) pincer complexes (M = Fe, Ru, Os; X = N, O, S) serve as catalyst lead structures for NH3 synthesis from N-2 and H-2?

AU - Holscher, M.

AU - Prechtl, Martin H. G.

AU - Leitner, W.

N1 - ISI Document Delivery No.: 199QQ Times Cited: 12 Cited Reference Count: 55 Cited References: Abdur-Rashid K, 2000, ORGANOMETALLICS, V19, P1652, DOI 10.1021/om990669i ANDRAE D, 1990, THEOR CHIM ACTA, V77, P1203 Aneetha H, 2002, ORGANOMETALLICS, V21, P628, DOI 10.1021/om010730v BECKE AD, 1993, J CHEM PHYS, V98, P5648, DOI 10.1063/1.464913 BOBADOVAPARVANO.Q, 2006, J AM CHEM SOC, V128, P11391 BOBADOVAPARVANO.Q, 2005, ANGEW CHEM, V117, P7263 Bobadova-Parvanova P, 2005, ANGEW CHEM INT EDIT, V44, P7101, DOI 10.1002/anie.200501371 CHATT J, 1978, CHEM REV, V78, P589, DOI 10.1021/cr60316a001 Clentsmith GKB, 1999, J AM CHEM SOC, V121, P10444, DOI 10.1021/ja9921219 Franke O, 2002, Z ANORG ALLG CHEM, V628, P2395, DOI 10.1002/1521-3749(200211)628:11<2395::AID-ZAAC2395>3.0.CO;2-M Frisch M. J., 2004, GAUSSIAN 03 REVISION Fryzuk MD, 2003, CHEM REC, V3, P2, DOI 10.1002/tcr.10044 Fryzuk MD, 1997, SCIENCE, V275, P1445, DOI 10.1126/science.275.5305.1445 Giunta D, 2003, ADV SYNTH CATAL, V345, P1139, DOI 10.1002/adsc.200303091 Gusev DG, 2000, ORGANOMETALLICS, V19, P3429, DOI 10.1021/om0003842 HAGGIN J, 1993, CHEM ENG NEWS, V71, P23, DOI 10.1021/cen-v071n022.p023 HENDERSON RA, 1982, J CHEM SOC DALTON, P917, DOI 10.1039/dt9820000917 HIDAI M, 1999, TOP ORGANOMET CHEM, V3, P227 Himmel H.-J., 2006, ANGEW CHEM, V118, P6412, DOI 10.1002/ange.200502892 Himmel HJ, 2006, ANGEW CHEM INT EDIT, V45, P6264, DOI 10.1002/anie.200502892 Holscher M, 2006, EUR J INORG CHEM, P4407, DOI 10.1002/ejic.200600548 Kozak CM, 2004, ANGEW CHEM INT EDIT, V43, P1186, DOI 10.1002/anie.200301712 KOZAK CM, 2004, ANGEW CHEM, V116, P1206, DOI 10.1002/ange.200301712 LEE CT, 1988, PHYS REV B, V37, P785, DOI 10.1103/PhysRevB.37.785 Le Guennic B, 2005, CHEM-EUR J, V11, P7448, DOI 10.1002/chem.200500935 MacKay BA, 2004, CHEM REV, V104, P385, DOI 10.1021/cr020610c Major Q, 2005, ORGANOMETALLICS, V24, P2492, DOI 10.1021/om050053v Miyachi H, 2005, J PHYS CHEM A, V109, P8800, DOI 10.1021/jp053308r Musaev DG, 2007, INORG CHEM, V46, P2709, DOI 10.1021/ic062405b Ohki Y, 2007, ANGEW CHEM INT EDIT, V46, P3180, DOI 10.1002/anie.200605245 Ohki Y., 2007, ANGEW CHEM, V119, P3242, DOI 10.1002/ange.200605245 Pool JA, 2004, NATURE, V427, P527, DOI 10.1038/nature02274 Prechtl M. H. G., 2007, ANGEW CHEM, V119, P2319, DOI 10.1002/ange.200603677 Prechtl MHG, 2007, CHEM-EUR J, V13, P1539, DOI 10.1002/chem.200600897 Prechtl MHG, 2007, ANGEW CHEM INT EDIT, V46, P2269, DOI 10.1002/anie.200603677 Reiher M, 2005, INORG CHEM, V44, P9640, DOI 10.1021/ic0517568 Ritleng V, 2004, J AM CHEM SOC, V126, P6150, DOI 10.1021/ja0306415 SCHAFER A, 1992, J CHEM PHYS, V97, P2571 SCHAFER A, 1994, J CHEM PHYS, V100, P5829 Schlogl R, 2003, ANGEW CHEM INT EDIT, V42, P2004, DOI 10.1002/anie.200301553 Schlogl R., 2003, ANGEW CHEM, V115, P2050, DOI 10.1002/ange.200301553 Schrock RR, 2005, ACCOUNTS CHEM RES, V38, P955, DOI 10.1021/ar0501121 Schrock RR, 2003, CHEM COMMUN, P2389, DOI 10.1039/b307784p Shaver MP, 2003, ADV SYNTH CATAL, V345, P1061, DOI 10.1002/adsc.200303081 STEPHENS PJ, 1994, J PHYS CHEM-US, V98, P11623, DOI 10.1021/j100096a001 Studt F, 2006, EUR J INORG CHEM, P291, DOI 10.1002/ejic.200500693 Studt F, 2006, J COMPUT CHEM, V27, P1278, DOI 10.1002/jcc.20413 Studt F, 2005, ANGEW CHEM INT EDIT, V44, P5639, DOI 10.1002/anie.200501485 Tomasi J, 2005, CHEM REV, V105, P2999, DOI 10.1021/cr9904009 VOSKO SH, 1980, CAN J PHYS, V58, P1200 Yandulov DV, 2003, INORG CHEM, V42, P796, DOI 10.1021/ic020505l Yandulov DV, 2005, INORG CHEM, V44, P1103, DOI 10.1021/ic040095w Yandulov DV, 2003, SCIENCE, V301, P76, DOI 10.1126/science.1085326 Yandulov DV, 2002, J AM CHEM SOC, V124, P6252, DOI 10.1021/ja020186x Zhang J, 2004, ORGANOMETALLICS, V23, P4026, DOI 10.1021/om049716j Hoelscher, Markus Prechtl, Martin H. G. Leitner, Walter Prechtl, Martin/A-7416-2008 Prechtl, Martin/0000-0003-2155-8006 12 Wiley-v c h verlag gmbh Weinheim

PY - 2007

Y1 - 2007

N2 - The potential of pincer complexes [M(H)(2)(H-2)(PXP)] (M=Fe, Ru, Os; X=N, O, S) to coordinate, activate, and thus catalyze the reaction of N-2 with classical or nonclassical hydrogen centers present at the metal center, with the aim of forming NH3 with H-2 as the only other reagent, was explored by means of DF (density functional) calculations. Screening of various complexes for their ability to perform initial hydrogen transfer to coordinated N-2 showed ruthenium pincer complexes to be more promising than the corresponding iron and osmium analogues. The ligand backbone influences the reaction dramatically: the presence of pyridine and thioether groups as backbones in the ligand result in inactive and result in unprecedented low activation barriers (23.7 and 22.1 kcal mol(-1), respectively), low enough to be interesting for practical application. Catalytic cycles were calculated for [Ru(H)(2)(H-2)(POP)] catalysts (POP= 2,5-bis(dimethylphosphanylmethyl)furan and 2,6-bis(dimethylphosphanylmethyl)-gamma-pyran). The height of activation barriers for the furan system is somewhat more advantageous. Formation of inactive metal nitrides has not been observed. SCRF calculations were used to introduce solvent (toluene) effects. The Gibbs free energies of activation of the numerous single reaction steps do not change significantly when solvent is included. The reaction steps associated with the formation of the active catalyst from precursors [M(H)(2)(H-2)(PXP)] were also calculated. The otherwise inactive pyridine ligand system allows for the generation of the active catalyst species, whereas the ether ligand systems show activation barriers that could prohibit practical application. Consequently the generation of the active catalyst species needs to be addressed in further studies.

AB - The potential of pincer complexes [M(H)(2)(H-2)(PXP)] (M=Fe, Ru, Os; X=N, O, S) to coordinate, activate, and thus catalyze the reaction of N-2 with classical or nonclassical hydrogen centers present at the metal center, with the aim of forming NH3 with H-2 as the only other reagent, was explored by means of DF (density functional) calculations. Screening of various complexes for their ability to perform initial hydrogen transfer to coordinated N-2 showed ruthenium pincer complexes to be more promising than the corresponding iron and osmium analogues. The ligand backbone influences the reaction dramatically: the presence of pyridine and thioether groups as backbones in the ligand result in inactive and result in unprecedented low activation barriers (23.7 and 22.1 kcal mol(-1), respectively), low enough to be interesting for practical application. Catalytic cycles were calculated for [Ru(H)(2)(H-2)(POP)] catalysts (POP= 2,5-bis(dimethylphosphanylmethyl)furan and 2,6-bis(dimethylphosphanylmethyl)-gamma-pyran). The height of activation barriers for the furan system is somewhat more advantageous. Formation of inactive metal nitrides has not been observed. SCRF calculations were used to introduce solvent (toluene) effects. The Gibbs free energies of activation of the numerous single reaction steps do not change significantly when solvent is included. The reaction steps associated with the formation of the active catalyst from precursors [M(H)(2)(H-2)(PXP)] were also calculated. The otherwise inactive pyridine ligand system allows for the generation of the active catalyst species, whereas the ether ligand systems show activation barriers that could prohibit practical application. Consequently the generation of the active catalyst species needs to be addressed in further studies.

KW - activation energy ammonia density functional calculations homogeneous catalysis pincer complexes ruthenium molybdenum triamidoamine complexes ruthenium hydride complexes gaussian-basis sets dinitrogen complexes metal-complexes nitrogen-fixation coordinate

U2 - 10.1002/chem.200700289

DO - 10.1002/chem.200700289

M3 - Journal article

VL - 13

SP - 6636

EP - 6643

JO - Chemistry: A European Journal

JF - Chemistry: A European Journal

SN - 0947-6539

IS - 23

ER -