Structural tungsten-imido chemistry: The gas-phase structure of W(NBu t)2(NHBut)2 and the solid-state structures of novel heterobimetallic W/N/M (M = Rh, Pd, Zn) species

H. Choujaa; S.D. Cosham; A.L. Johnson; G.R. Kafka; M.F. Mahon; S.L. Masters; K.C. Molloy; D.W.H. Rankin; H.E. Robertson; D.A. Wann

doi:10.1021/ic8021134

Structural tungsten-imido chemistry: The gas-phase structure of W(NBu t)2(NHBut)2 and the solid-state structures of novel heterobimetallic W/N/M (M = Rh, Pd, Zn) species

H. Choujaa, S.D. Cosham, A.L. Johnson, G.R. Kafka, M.F. Mahon, S.L. Masters, K.C. Molloy, D.W.H. Rankin, H.E. Robertson, D.A. Wann

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The gas-phase (electron diffraction) and solid-state (X-ray) structures of W(NBut)2(NHBut)2 (1) have been determined. In the gas phase, 1 adopts both C1 and C2 conformations in a 69:31 ratio. The solid-state structure is disordered over two equal sites, both showing approximate C2 conformation as in the gas phase; the imido and amido centers are, however, clearly distinguished. Compound 1 has been used to synthesize novel heterobimetallic derivatives W(NBu t)4[Rh(COD)]2 (3) and W(NBut) 4[Pd(η3-C3H5)]2 (4) via the dilithiated intermediate Li2[W(NBut) 4](2). In both cases, the [W(NBut)4] moiety bridges the two organometallic fragments. Reaction of 1 with Me2Zn has produced [Me(tBuN)W(μ-NBut)2ZnMe(NH 2But)] (5). The structures of 3, 4, and 5 have been determined. Thermal decomposition of 4 under an autogenerated pressure at 700 °C has formed the hitherto uncharacterized bimetallic alloy WPd2. © 2009 American Chemical Society.

Original language	Undefined/Unknown
Pages (from-to)	2289-2299
Number of pages	11
Journal	Inorganic Chemistry
Volume	48
Issue number	5
DOIs	https://doi.org/10.1021/ic8021134
Publication status	Published - 2 Mar 2009

Bibliographical note

Cited By (since 1996):2

Export Date: 1 October 2013

Source: Scopus

CODEN: INOCA

doi: 10.1021/ic8021134

Language of Original Document: English

Correspondence Address: Mahon, M. F.; Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom; email: [email protected]

References: Nugent, W.A., Haymore, B.L., (1980) Coord. Chem. Rev, 31, p. 123; McElwee-White, L., (2006) Dalton Trans, p. 5327; Potts, S.E., Carmalt, C.J., Blackman, C.S., Leese, T., Davies, H.O., (2008) Dalton Trans, p. 5730; Nugent, W.A., (1983) Inorg. Chem, 22, p. 965; Nugent, W.A., Harlow, R.L., (1980) Inorg. Chem, 19, p. 777; Danopoulos, A.A., Wilkinson, G., Hussain, B., Hursthouse, M.B., (1989) J. Chem. Soc., Chem. Commun, p. 896; Danopoulos, A.A., Wilkinson, G., Hussain-Bates, B., Hursthouse, M.B., (1990) J. Chem. Soc., Dalton Trans, p. 2753; Danopoulos, A.A., Wilkinson, G., Sweet, T.K.N., Hursthouse, M.B., (1994) Polyhedron, 13, p. 2899; Becker, J.S., Gordon, R.G., (2003) Appl. Phys. Lett, 82, p. 2239; Becker, J.S., Suh, S., Wang, S., Gordon, R.G., (2003) Chem. Mater, 15, p. 2969; El-Kadri, O.M., Heeg, M.J., Winter, C.H., (2006) Dalton Trans, p. 1943; Yang, Y.-W., Wu, J.-B., Wang, J., Lin, Y.-F., Chiu, H.-T., (2006) Surf. Sci, 600, p. 743; Currie, A.L., Howard, K.E., (1992) J. Mater. Sci, 27, p. 2739; Crane, E.L., Chiu, H.-T., Nuzzo, R.G., (2001) J. Phys. Chem. B, 105, p. 3549; Tsai, M.H., Sun, S.C., Chiu, H.T., Chuang, S.H., (1996) Appl. Phys. Lett, 68, p. 1412; Chiu, H.-T., Chuang, S.-H., (1993) J. Mater. Res, 8, p. 1353; Chiu, H.-T., Chuang, S.-H., Lee, G.-H., Peng, S.-M., (1994) Polyhedron, 13, p. 2443; There is a discrepancy in ref 4 relating to the cell parameters for W(NBut)2(NHBut)2, where they are reported erroneously (monoclinic, C2, a = 21.000, b = 7.602, c = 14.852 Å, β = 106.89°). These data probably refer to the compound (Me3SiO)2Cr(NBut)2, as the crystal- lographic data quoted for this compound are essentially identical to what we now report for 1De Lima, G.M., Duncalf, D.J., (1999) Organometallics, 18, p. 4884; Gosink, H.-J., Roesky, H.W., Schmidt, H.-G., Noltemeyer, M., Irmer, E., Herbst-Irmer, R., (1994) Organometallics, 13, p. 3420; http://www.nsccs.ac.uk, National Service for Computational Chemistry Software NSCCSFrisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Zakrzewski, V. G, Montgomery, J. J. A, Stratmann, R. E, Burant, J. C, Dapprich, S, Millam, J. M, Daniel, A. D, Kudin, K. N, Strain, M. C, Farkas, O, Tomasi, J, Barone, V, Cossi, M, Cammi, R, Mennucci, B, Pomelli, C, Adamo, C, Clifford, S, Ochterski, J, Petersson, G. A, Ayala, P. Y, Cui, Q, Morokuma, K, Rega, N, Salvador, P, Dannenberg, J. J, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Cioslowski, J, Ortiz, J. V, Baboul, A. G, Stefanov, B. B, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Gomperts, R, Martin, R. L, Fox, D. J, Keith, T, Al-Laham, M. A, Peng, C. Y, Nanayakkara, A, Challacombe, M, Gill, P. M. W, Johnson, B, Chen, W, Wong, M. W, Andres, J. L, Gonzalez, C, Head-Gordon, M, Replogle, E. S, Pople, J. A. Gaussian 03; Gaussian, Inc, Wallingford, CT, 2004Sipachev, V.A., (1985) J. Mol. Struct. (THEOCHEM), 121, p. 143; Sipachev, V.A., (2001) J. Mol. Struct, 567, p. 67; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc., Dalton Trans, p. 954; Fleischer, H., Wann, D.A., Hinchley, S.L., Borisenko, K.B., Lewis, J.R., Mawhorter, R.J., Robertson, H.E., Rankin, D.W.H., (2005) Dalton Trans, p. 3221; Hinchley, S.L., Robertson, H.E., Borisenko, K.B., Turner, A.R., Johnston, B.F., Rankin, D.W.H., Ahmadian, M., Cowley, A.H., (2004) Dalton Trans, p. 2469; Ross, A.W., Fink, M., Hilderbrand, R., (1992) International Tables for Crystallography, , Kluwer Academic Publishers: Dordrecht; Barbour, L.J., (2001) J. Supramol. Chem, 1, p. 189; Pol, S.V., Pol, V.G., Gedanken, L., (2004) Chem.-Eur. J, 10, p. 4467; Blake, A.J., Brain, P.T., McNab, H., Miller, J., Morrison, C.A., Parsons, S., Rankin, D.W.H., Smart, B.A., (1996) J. Chem. Phys, 100, p. 12280; Brain, P.T., Morrison, C.A., Parsons, S., Rankin, D.W.H., (1996) J. Chem. Soc., Dalton Trans, p. 4589; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans, p. 3650; Hamilton, W.C., (1965) Acta Crystallogr, 18, p. 502; Seip, H.M., (1965) Acta Chem. Scand, 19, p. 1955; Jacob, E.J., Bartell, L.S., (1970) J. Chem. Phys, 53, p. 2231; Emsley, J., (1989) The Elements, , Clarendon Press: Oxford, U.K; Mann, B.E., Pietropaolo, R., Shaw, B.L., (1973) J. Chem. Soc., Dalton Trans, p. 2390; Chan, D.M.-T., Fultz, W.C., Nugent, W.A., Roe, D.C., Tulip, T.H., (1985) J. Am. Chem. Soc, 107, p. 251; Legzdins, P., Ross, K.J., Sayers, S.F., Rettig, S.J., (1997) Organometallics, 16, p. 190; Bond, A.D., Hopkins, A.D., Rothenberger, A., Wolf, R., Woods, A.D., Wright, D.S., (2001) Organometallics, 20, p. 4454; Ward, B.D., Orde, G., Clot, E., Cowley, A.R., Gade, L.H., Mountford, P., (2004) Organometallics, 23, p. 4444; Westerhausen, M., Bollwein, T., Pfitzner, A., Nilges, T., Deiseroth, H.-J., (2001) Inorg. Chim. Acta, 312, p. 239; Odani, A., Pol, V.G., Pol, S.V., Koltypin, M., Gedanken, A., Aurbach, D., (2006) Adv. Mater, 18, p. 1431; Pol, S.V., Pol, V.G., Kessler, V.G., Seisenbaeva, G.A., Sung, M., Asai, S., Gedanken, A., (2004) J. Phys. Chem. B, 108, p. 6322; Pol, S.V., Pol, V.G., Kessler, V.G., Gedanken, A., (2006) New J. Chem, 30, p. 370; Neuimina, S.V., Zhmurko, G.P., Kalmykov, K.B., Sokolovskaya, E.M., Kuznetsov, V.N., (1992) Vestn. Mosk. Univ., Ser: Khim, 33, p. 57; Hollingsworth, N., Kanna, M., Kociok-Köhn, G., Molloy, K.C., Wongnawa, S., (2008) Dalton Trans, p. 631

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Cite this

Choujaa, H., Cosham, S. D., Johnson, A. L., Kafka, G. R., Mahon, M. F., Masters, S. L., Molloy, K. C., Rankin, D. W. H., Robertson, H. E., & Wann, D. A. (2009). Structural tungsten-imido chemistry: The gas-phase structure of W(NBu t)2(NHBut)2 and the solid-state structures of novel heterobimetallic W/N/M (M = Rh, Pd, Zn) species. Inorganic Chemistry, 48(5), 2289-2299. https://doi.org/10.1021/ic8021134

@article{4ef5e023f83c49169caabe899745095f,

title = "Structural tungsten-imido chemistry: The gas-phase structure of W(NBu t)2(NHBut)2 and the solid-state structures of novel heterobimetallic W/N/M (M = Rh, Pd, Zn) species",

abstract = "The gas-phase (electron diffraction) and solid-state (X-ray) structures of W(NBut)2(NHBut)2 (1) have been determined. In the gas phase, 1 adopts both C1 and C2 conformations in a 69:31 ratio. The solid-state structure is disordered over two equal sites, both showing approximate C2 conformation as in the gas phase; the imido and amido centers are, however, clearly distinguished. Compound 1 has been used to synthesize novel heterobimetallic derivatives W(NBu t)4[Rh(COD)]2 (3) and W(NBut) 4[Pd(η3-C3H5)]2 (4) via the dilithiated intermediate Li2[W(NBut) 4](2). In both cases, the [W(NBut)4] moiety bridges the two organometallic fragments. Reaction of 1 with Me2Zn has produced [Me(tBuN)W(μ-NBut)2ZnMe(NH 2But)] (5). The structures of 3, 4, and 5 have been determined. Thermal decomposition of 4 under an autogenerated pressure at 700 °C has formed the hitherto uncharacterized bimetallic alloy WPd2. {\textcopyright} 2009 American Chemical Society.",

author = "H. Choujaa and S.D. Cosham and A.L. Johnson and G.R. Kafka and M.F. Mahon and S.L. Masters and K.C. Molloy and D.W.H. Rankin and H.E. Robertson and D.A. Wann",

note = "Cited By (since 1996):2 Export Date: 1 October 2013 Source: Scopus CODEN: INOCA doi: 10.1021/ic8021134 Language of Original Document: English Correspondence Address: Mahon, M. F.; Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom; email: [email protected] References: Nugent, W.A., Haymore, B.L., (1980) Coord. Chem. Rev, 31, p. 123; McElwee-White, L., (2006) Dalton Trans, p. 5327; Potts, S.E., Carmalt, C.J., Blackman, C.S., Leese, T., Davies, H.O., (2008) Dalton Trans, p. 5730; Nugent, W.A., (1983) Inorg. Chem, 22, p. 965; Nugent, W.A., Harlow, R.L., (1980) Inorg. Chem, 19, p. 777; Danopoulos, A.A., Wilkinson, G., Hussain, B., Hursthouse, M.B., (1989) J. Chem. Soc., Chem. Commun, p. 896; Danopoulos, A.A., Wilkinson, G., Hussain-Bates, B., Hursthouse, M.B., (1990) J. Chem. Soc., Dalton Trans, p. 2753; Danopoulos, A.A., Wilkinson, G., Sweet, T.K.N., Hursthouse, M.B., (1994) Polyhedron, 13, p. 2899; Becker, J.S., Gordon, R.G., (2003) Appl. Phys. Lett, 82, p. 2239; Becker, J.S., Suh, S., Wang, S., Gordon, R.G., (2003) Chem. Mater, 15, p. 2969; El-Kadri, O.M., Heeg, M.J., Winter, C.H., (2006) Dalton Trans, p. 1943; Yang, Y.-W., Wu, J.-B., Wang, J., Lin, Y.-F., Chiu, H.-T., (2006) Surf. Sci, 600, p. 743; Currie, A.L., Howard, K.E., (1992) J. Mater. Sci, 27, p. 2739; Crane, E.L., Chiu, H.-T., Nuzzo, R.G., (2001) J. Phys. Chem. B, 105, p. 3549; Tsai, M.H., Sun, S.C., Chiu, H.T., Chuang, S.H., (1996) Appl. Phys. Lett, 68, p. 1412; Chiu, H.-T., Chuang, S.-H., (1993) J. Mater. Res, 8, p. 1353; Chiu, H.-T., Chuang, S.-H., Lee, G.-H., Peng, S.-M., (1994) Polyhedron, 13, p. 2443; There is a discrepancy in ref 4 relating to the cell parameters for W(NBut)2(NHBut)2, where they are reported erroneously (monoclinic, C2, a = 21.000, b = 7.602, c = 14.852 {\AA}, β = 106.89°). These data probably refer to the compound (Me3SiO)2Cr(NBut)2, as the crystal- lographic data quoted for this compound are essentially identical to what we now report for 1De Lima, G.M., Duncalf, D.J., (1999) Organometallics, 18, p. 4884; Gosink, H.-J., Roesky, H.W., Schmidt, H.-G., Noltemeyer, M., Irmer, E., Herbst-Irmer, R., (1994) Organometallics, 13, p. 3420; http://www.nsccs.ac.uk, National Service for Computational Chemistry Software NSCCSFrisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Zakrzewski, V. G, Montgomery, J. J. A, Stratmann, R. E, Burant, J. C, Dapprich, S, Millam, J. M, Daniel, A. D, Kudin, K. N, Strain, M. C, Farkas, O, Tomasi, J, Barone, V, Cossi, M, Cammi, R, Mennucci, B, Pomelli, C, Adamo, C, Clifford, S, Ochterski, J, Petersson, G. A, Ayala, P. Y, Cui, Q, Morokuma, K, Rega, N, Salvador, P, Dannenberg, J. J, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Cioslowski, J, Ortiz, J. V, Baboul, A. G, Stefanov, B. B, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Gomperts, R, Martin, R. L, Fox, D. J, Keith, T, Al-Laham, M. A, Peng, C. Y, Nanayakkara, A, Challacombe, M, Gill, P. M. W, Johnson, B, Chen, W, Wong, M. W, Andres, J. L, Gonzalez, C, Head-Gordon, M, Replogle, E. S, Pople, J. A. Gaussian 03; Gaussian, Inc, Wallingford, CT, 2004Sipachev, V.A., (1985) J. Mol. Struct. (THEOCHEM), 121, p. 143; Sipachev, V.A., (2001) J. Mol. Struct, 567, p. 67; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc., Dalton Trans, p. 954; Fleischer, H., Wann, D.A., Hinchley, S.L., Borisenko, K.B., Lewis, J.R., Mawhorter, R.J., Robertson, H.E., Rankin, D.W.H., (2005) Dalton Trans, p. 3221; Hinchley, S.L., Robertson, H.E., Borisenko, K.B., Turner, A.R., Johnston, B.F., Rankin, D.W.H., Ahmadian, M., Cowley, A.H., (2004) Dalton Trans, p. 2469; Ross, A.W., Fink, M., Hilderbrand, R., (1992) International Tables for Crystallography, , Kluwer Academic Publishers: Dordrecht; Barbour, L.J., (2001) J. Supramol. Chem, 1, p. 189; Pol, S.V., Pol, V.G., Gedanken, L., (2004) Chem.-Eur. J, 10, p. 4467; Blake, A.J., Brain, P.T., McNab, H., Miller, J., Morrison, C.A., Parsons, S., Rankin, D.W.H., Smart, B.A., (1996) J. Chem. Phys, 100, p. 12280; Brain, P.T., Morrison, C.A., Parsons, S., Rankin, D.W.H., (1996) J. Chem. Soc., Dalton Trans, p. 4589; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans, p. 3650; Hamilton, W.C., (1965) Acta Crystallogr, 18, p. 502; Seip, H.M., (1965) Acta Chem. Scand, 19, p. 1955; Jacob, E.J., Bartell, L.S., (1970) J. Chem. Phys, 53, p. 2231; Emsley, J., (1989) The Elements, , Clarendon Press: Oxford, U.K; Mann, B.E., Pietropaolo, R., Shaw, B.L., (1973) J. Chem. Soc., Dalton Trans, p. 2390; Chan, D.M.-T., Fultz, W.C., Nugent, W.A., Roe, D.C., Tulip, T.H., (1985) J. Am. Chem. Soc, 107, p. 251; Legzdins, P., Ross, K.J., Sayers, S.F., Rettig, S.J., (1997) Organometallics, 16, p. 190; Bond, A.D., Hopkins, A.D., Rothenberger, A., Wolf, R., Woods, A.D., Wright, D.S., (2001) Organometallics, 20, p. 4454; Ward, B.D., Orde, G., Clot, E., Cowley, A.R., Gade, L.H., Mountford, P., (2004) Organometallics, 23, p. 4444; Westerhausen, M., Bollwein, T., Pfitzner, A., Nilges, T., Deiseroth, H.-J., (2001) Inorg. Chim. Acta, 312, p. 239; Odani, A., Pol, V.G., Pol, S.V., Koltypin, M., Gedanken, A., Aurbach, D., (2006) Adv. Mater, 18, p. 1431; Pol, S.V., Pol, V.G., Kessler, V.G., Seisenbaeva, G.A., Sung, M., Asai, S., Gedanken, A., (2004) J. Phys. Chem. B, 108, p. 6322; Pol, S.V., Pol, V.G., Kessler, V.G., Gedanken, A., (2006) New J. Chem, 30, p. 370; Neuimina, S.V., Zhmurko, G.P., Kalmykov, K.B., Sokolovskaya, E.M., Kuznetsov, V.N., (1992) Vestn. Mosk. Univ., Ser: Khim, 33, p. 57; Hollingsworth, N., Kanna, M., Kociok-K{\"o}hn, G., Molloy, K.C., Wongnawa, S., (2008) Dalton Trans, p. 631",

year = "2009",

month = mar,

day = "2",

doi = "10.1021/ic8021134",

language = "Undefined/Unknown",

volume = "48",

pages = "2289--2299",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "5",

}

Choujaa, H, Cosham, SD, Johnson, AL, Kafka, GR, Mahon, MF, Masters, SL, Molloy, KC, Rankin, DWH, Robertson, HE & Wann, DA 2009, 'Structural tungsten-imido chemistry: The gas-phase structure of W(NBu t)2(NHBut)2 and the solid-state structures of novel heterobimetallic W/N/M (M = Rh, Pd, Zn) species', Inorganic Chemistry, vol. 48, no. 5, pp. 2289-2299. https://doi.org/10.1021/ic8021134

TY - JOUR

T1 - Structural tungsten-imido chemistry: The gas-phase structure of W(NBu t)2(NHBut)2 and the solid-state structures of novel heterobimetallic W/N/M (M = Rh, Pd, Zn) species

AU - Choujaa, H.

AU - Cosham, S.D.

AU - Johnson, A.L.

AU - Kafka, G.R.

AU - Mahon, M.F.

AU - Masters, S.L.

AU - Molloy, K.C.

AU - Rankin, D.W.H.

AU - Robertson, H.E.

AU - Wann, D.A.

N1 - Cited By (since 1996):2 Export Date: 1 October 2013 Source: Scopus CODEN: INOCA doi: 10.1021/ic8021134 Language of Original Document: English Correspondence Address: Mahon, M. F.; Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom; email: [email protected] References: Nugent, W.A., Haymore, B.L., (1980) Coord. Chem. Rev, 31, p. 123; McElwee-White, L., (2006) Dalton Trans, p. 5327; Potts, S.E., Carmalt, C.J., Blackman, C.S., Leese, T., Davies, H.O., (2008) Dalton Trans, p. 5730; Nugent, W.A., (1983) Inorg. Chem, 22, p. 965; Nugent, W.A., Harlow, R.L., (1980) Inorg. Chem, 19, p. 777; Danopoulos, A.A., Wilkinson, G., Hussain, B., Hursthouse, M.B., (1989) J. Chem. Soc., Chem. Commun, p. 896; Danopoulos, A.A., Wilkinson, G., Hussain-Bates, B., Hursthouse, M.B., (1990) J. Chem. Soc., Dalton Trans, p. 2753; Danopoulos, A.A., Wilkinson, G., Sweet, T.K.N., Hursthouse, M.B., (1994) Polyhedron, 13, p. 2899; Becker, J.S., Gordon, R.G., (2003) Appl. Phys. Lett, 82, p. 2239; Becker, J.S., Suh, S., Wang, S., Gordon, R.G., (2003) Chem. Mater, 15, p. 2969; El-Kadri, O.M., Heeg, M.J., Winter, C.H., (2006) Dalton Trans, p. 1943; Yang, Y.-W., Wu, J.-B., Wang, J., Lin, Y.-F., Chiu, H.-T., (2006) Surf. Sci, 600, p. 743; Currie, A.L., Howard, K.E., (1992) J. Mater. Sci, 27, p. 2739; Crane, E.L., Chiu, H.-T., Nuzzo, R.G., (2001) J. Phys. Chem. B, 105, p. 3549; Tsai, M.H., Sun, S.C., Chiu, H.T., Chuang, S.H., (1996) Appl. Phys. Lett, 68, p. 1412; Chiu, H.-T., Chuang, S.-H., (1993) J. Mater. Res, 8, p. 1353; Chiu, H.-T., Chuang, S.-H., Lee, G.-H., Peng, S.-M., (1994) Polyhedron, 13, p. 2443; There is a discrepancy in ref 4 relating to the cell parameters for W(NBut)2(NHBut)2, where they are reported erroneously (monoclinic, C2, a = 21.000, b = 7.602, c = 14.852 Å, β = 106.89°). These data probably refer to the compound (Me3SiO)2Cr(NBut)2, as the crystal- lographic data quoted for this compound are essentially identical to what we now report for 1De Lima, G.M., Duncalf, D.J., (1999) Organometallics, 18, p. 4884; Gosink, H.-J., Roesky, H.W., Schmidt, H.-G., Noltemeyer, M., Irmer, E., Herbst-Irmer, R., (1994) Organometallics, 13, p. 3420; http://www.nsccs.ac.uk, National Service for Computational Chemistry Software NSCCSFrisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Zakrzewski, V. G, Montgomery, J. J. A, Stratmann, R. E, Burant, J. C, Dapprich, S, Millam, J. M, Daniel, A. D, Kudin, K. N, Strain, M. C, Farkas, O, Tomasi, J, Barone, V, Cossi, M, Cammi, R, Mennucci, B, Pomelli, C, Adamo, C, Clifford, S, Ochterski, J, Petersson, G. A, Ayala, P. Y, Cui, Q, Morokuma, K, Rega, N, Salvador, P, Dannenberg, J. J, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Cioslowski, J, Ortiz, J. V, Baboul, A. G, Stefanov, B. 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Supramol. Chem, 1, p. 189; Pol, S.V., Pol, V.G., Gedanken, L., (2004) Chem.-Eur. J, 10, p. 4467; Blake, A.J., Brain, P.T., McNab, H., Miller, J., Morrison, C.A., Parsons, S., Rankin, D.W.H., Smart, B.A., (1996) J. Chem. Phys, 100, p. 12280; Brain, P.T., Morrison, C.A., Parsons, S., Rankin, D.W.H., (1996) J. Chem. Soc., Dalton Trans, p. 4589; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans, p. 3650; Hamilton, W.C., (1965) Acta Crystallogr, 18, p. 502; Seip, H.M., (1965) Acta Chem. Scand, 19, p. 1955; Jacob, E.J., Bartell, L.S., (1970) J. Chem. Phys, 53, p. 2231; Emsley, J., (1989) The Elements, , Clarendon Press: Oxford, U.K; Mann, B.E., Pietropaolo, R., Shaw, B.L., (1973) J. Chem. Soc., Dalton Trans, p. 2390; Chan, D.M.-T., Fultz, W.C., Nugent, W.A., Roe, D.C., Tulip, T.H., (1985) J. Am. Chem. 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PY - 2009/3/2

Y1 - 2009/3/2

N2 - The gas-phase (electron diffraction) and solid-state (X-ray) structures of W(NBut)2(NHBut)2 (1) have been determined. In the gas phase, 1 adopts both C1 and C2 conformations in a 69:31 ratio. The solid-state structure is disordered over two equal sites, both showing approximate C2 conformation as in the gas phase; the imido and amido centers are, however, clearly distinguished. Compound 1 has been used to synthesize novel heterobimetallic derivatives W(NBu t)4[Rh(COD)]2 (3) and W(NBut) 4[Pd(η3-C3H5)]2 (4) via the dilithiated intermediate Li2[W(NBut) 4](2). In both cases, the [W(NBut)4] moiety bridges the two organometallic fragments. Reaction of 1 with Me2Zn has produced [Me(tBuN)W(μ-NBut)2ZnMe(NH 2But)] (5). The structures of 3, 4, and 5 have been determined. Thermal decomposition of 4 under an autogenerated pressure at 700 °C has formed the hitherto uncharacterized bimetallic alloy WPd2. © 2009 American Chemical Society.

AB - The gas-phase (electron diffraction) and solid-state (X-ray) structures of W(NBut)2(NHBut)2 (1) have been determined. In the gas phase, 1 adopts both C1 and C2 conformations in a 69:31 ratio. The solid-state structure is disordered over two equal sites, both showing approximate C2 conformation as in the gas phase; the imido and amido centers are, however, clearly distinguished. Compound 1 has been used to synthesize novel heterobimetallic derivatives W(NBu t)4[Rh(COD)]2 (3) and W(NBut) 4[Pd(η3-C3H5)]2 (4) via the dilithiated intermediate Li2[W(NBut) 4](2). In both cases, the [W(NBut)4] moiety bridges the two organometallic fragments. Reaction of 1 with Me2Zn has produced [Me(tBuN)W(μ-NBut)2ZnMe(NH 2But)] (5). The structures of 3, 4, and 5 have been determined. Thermal decomposition of 4 under an autogenerated pressure at 700 °C has formed the hitherto uncharacterized bimetallic alloy WPd2. © 2009 American Chemical Society.

U2 - 10.1021/ic8021134

DO - 10.1021/ic8021134

M3 - Article

SN - 0020-1669

VL - 48

SP - 2289

EP - 2299

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 5

ER -