R.L. Keiter et al. / Inorganica Chimica Acta 364 (2010) 176–184
183
(c) R.L. Keiter, Y.Y. Sun, J.W. Brodack, L.W. Cary, J. Am. Chem. Soc. 101 (1979)
2638.
[4] J.L. Brookham, W. McFarlane, I.J. Colquhoun, J. Chem. Soc., Dalton Trans. (1988)
503.
[5] R.L. Keiter, J.W. Benson, E.A. Keiter, W. Lin, Z. Jia, D.M. Olson, D.E. Brandt, J.L.
Wheeler, Organometallics 17 (1998) 4291.
[6] (a) R.L. Keiter, J.W. Benson, Z. Jia, E.A. Keiter, D.E. Brandt, Organometallics 19
(2000) 4518;
It has been established that the acetate ligand in
[W(CO)5(O2CCH3)]ꢀ is cis-labilizing when PR3 replaces a CO ligand
to give cis-[W(CO)4(PR3)(O2CCH3)]ꢀ. It has been suggested that the
distal oxygen atom of the acetate ligand interacts with and dis-
places a cis carbonyl ligand to give cis-W(OC)4(j
2-O2CCH3)]ꢀ as a
first step. The solid state structure of [W(CO)5(O2CCH3)]ꢀ shows
that the separation between the distal oxygen atom and the carbon
of a cis carbonyl ligand is less than the sum of the Van der Waals
radii [35]. Close approaches of pendant thiolate and sulfinato
nucleophiles to CO ligands in tungsten pentacarbonyl complexes
are viewed as non-bonding but the degree to which they might en-
hance CO lability is unclear at this point [36].
To account for the oxidation of the terminal phosphine group of
[Re2(CO)9(r1-P-P) (P–P = ditertiary phosphine) by Me3NO, an intra-
molecular mechanism has been proposed that includes interaction
of the uncoordinated phosphine group with a carbonyl ligand. The
interaction activates phosphorus for nucleophilic attack by Me3NO,
leading to formation of [Re2(CO)9(r1-P–P@O)] [37].
Interaction of a dangling nucleophile with a bound carbonyl
group also appears to play a role in facilitating the reaction of CO
with the 18-electron Cp*Ru[HC(PPh2NPh)2] to give Cp*Ru[HC(PPh2
NPh)2CO]. In this instance a Ru–N bond is broken for Ru–CO
bond formation and the nitrogen of PPh2@NRh interacts with the
coordinated CO [38].
(b) K. Maitra, V.J. Catalano, J.H. Nelson, J. Organomet. Chem. 529 (1997)
409.
[7] I.J. Colquhoun, W. McFarlane, J. Chem. Soc., Dalton Trans. (1982) 1915.
[8] (a) S.J. Higgins, B.L. Shaw, J. Chem. Soc., Dalton Trans. (1989) 1527;
(b) G. King, S.J. Higgins, A. Hopton, ibid (1992) 3403.
[9] R.L. Keiter, J.W. Brodack, R.D. Borger, L.W. Cary, Inorg. Chem. 21 (1982) 1256.
[10] W.D. Covey, T.L. Brown, Inorg. Chem. 12 (1973) 2820.
[11] R.J. Angelici, Sister M.D. Malone, Inorg. Chem. 6 (1967) 1731.
[12] H. Schmidbaur, C. Paschalidis, G. Reber, G. Muller, Chem. Ber. 121 (1988) 1241.
[13] J.R. Sowa, R.J. Angelici, Inorg. Chem. 30 (1991) 3534.
[14] J.H. Espenson, Chemical Kinetics and Reaction Mechanisms, second ed.,
McGraw Hill, New York, 1995.
[15] J.R. Graham, R.J. Angelici, Inorg. Chem. 6 (1967) 2082.
[16] (a) A. Shagal, R.H. Schultz, Organometallics 21 (2002) 5657;
(b) A. Shagal, R.H. Schultz, ibid 26 (2007) 4896;
(c) S. Wieland, R. van Eldik, Organometallics 10 (1991) 3110;
(d) A.W. Ehlers, G. Frenking, J. Am. Chem. Soc. 116 (1994) 1514.
[17] (a) P.B. Dias, M.E. Minas da Pierdade, J.A. Martino Simões, Coord. Chem. Rev.
135/136 (1994) 737;
(b) S.L. Mukerjee, R.F. Lang, T. Ju, G. Kiss, C.D. Hoff, S.P. Nolan, Inorg. Chem. 31
(1992) 4885.
[18] G.K. Yang, K.S. Peters, V. Vaida, Chem. Phys. Lett. 125 (1986) 566.
[19] J.L. Brookham, W. McFarlane, M. Thornton-Pett, J. Chem. Soc., Dalton Trans.
(1992) 2353.
[20] (a) H. Schmidbaur, G. Reber, A. Schier, F.E. Wagner, G. Müller, Inorg. Chim. Acta
147 (1988) 143;
4. Conclusions
(b) C. Di Nicola, F.F. Effendy, C. Pettinari, B.W. Skelton, N. Somers, A.H. White,
Inorg. Chim. Acta 358 (2005) 720;
In this work we have presented kinetic, thermodynamic and
structural evidence to support a mechanism for exchange of coor-
dinated and uncoordinated arms of di- and tritertiary phosphines
in pentacarbonyl complexes of group 6 metals. The initial step in-
volves nucleophilic attack of a pendant phosphine on a carbonyl li-
gand, leading to dissociation of a coordinated phosphine. The rate-
determining step for 3M is a slow 1,2-shift leading to its linkage
isomer, 4M. For complexes 1M, a 1,2 shift is also possible but a
much faster pathway is available. This entails coordination of the
second dangling arm to give a 5-membered ring which opens to
give 2M.
(c) R.A. Burrow, F.C. Wouters, L. Borges de Castro, C. Peppe, Acta Crystallotr.,
Sect. E 63 (2007) 2559.
[21] (a) H. Schmidbaur, R. Herr, J. Riede, Chem. Ber. 117 (1984) 2322;
(b) J. Bruckmann, C. Krüger, F. Lutz, Z. Naturforsch. B 50 (1995) 351.
[22] (a) J.W. Benson, R.L. Keiter, E.A. Keiter, A.L. Rheingold, G.P.A. Yap, V.V. Mainz,
Organometallics 17 (1998) 4275;
(b) M.E. Rottick, R.J. Angelici, Inorg. Chem. 32 (1993) 2421.
[23] I.J. Colquhoun, W. McFarlane, J. Chem. Soc. (1982) 484.
[24] K. Eichele, G.C. Ossenkamp, R.E. Wasylishen, T.S. Cameron, Inorg. Chem. 38
(1999) 639 (The P–C–P angle in (OC)5Mo(j
1-dppm) is also 111°).
[25] (a) G.W. Wong, J.L. Harkreader, C.A. Mebi, B.J. Frost, Inorg. Chem. 45 (2006)
6748;
(b) G. Hogarth, J. Kilmartin, J. Organomet. Chem. 692 (2007) 5655.
[26] (a) A. Bondi, J. Phys. Chem. 68 (1964) 441;
(b) J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry: Principles of
Structure and Reactivity, fourth ed., HarperCollins, New York, 1993.
For other van der Waals radii estimates, see:
The close approach of a pendant phosphine to the bound car-
bonyl group in 2W and 8W may account in part for the observed
4-bond spin–spin coupling between phosphorus and carbon as
well as the 3-bond tungsten–phosphorus coupling.
(c) R.S. Rowland, R. Taylor, J. Phys. Chem. 100 (1996) 7384;
(d) I.A. Guzei, M. Wendt, Dalton Trans. (2006) 3991.
[27] (a) T.L. Brown, Inorg. Chem. 31 (1992) 1286;
(b) T.K. Woo, T. Ziegler, Inorg. Chem. 33 (1994) 1857.
[28] J.F. Hartwig, Organotransition Metal Chemistry, University Science Books,
Sausalito, CA, 2010.
5. Supplementary material
[29] (a) J.-C. Hierso, D. Evrard, D. Lucas, P. Richard, H. Cattey, B. Hanquet, J. Meunier,
J. Organomet. Chem. 693 (2008) 574;
CCDC 776107 and 776108 contain the supplementary crystallo-
graphic data. These data can be obtained free of charge from The
(b) J.C. Hierso, A. Fihri, V.V. Ivanov, B. Hanquet, N. Pirio, B. Donnadieu, B.
Rebiêre, R. Amardeil, P. Meuenier, J. Am. Chem. Soc. 124 (2004) 11077;
(c) R.H. Contreras, V.A. Barone, J. Facelli, J.E. Peralta, Ann. Rep. NMR Spectrosc.
51 (2003) 167;
(d) B.E. Cowie, D.J.H. Emslie, H.A. Jenkins, J.F. Britten, Inorg. Chem. 49 (2010)
4060.
[30] (a) A.E. Reed, L.A. Curtiss, F. Weinhold, Chem. Rev. 88 (1988) 899;
(b) H.B. Bürgi, J.D. Dunitz, Acc. Chem. Res. 16 (1983) 152.
[31] E.W. Abel, K.G. Orrell, H. Rahoo, V. Sik, J. Organomet. Chem. 441 (1992)
441.
[32] (a) S.W. Kirtley, in: G. Wilkinson, F.G.A. Stone, E.W. Abel (Eds.),
Comprehensive Organometallic Chemistry, vol. 3, Pergamon Press, New
York, 1982;
Acknowledgments
We are grateful to Chuck Casey for his keen insight and helpful
discussions and to Jeremy Wheeler for assistance in the integration
of some P-31 NMR spectra. We thank the Camille and Henry Dreyfus
Foundation for a Scholar/Fellow grant (SF-98-004) and the National
Science Foundation (CHE-9708342) for support of this work.
(b) E.O. Fischer, F.R. Kreissel, C.G. Kreiter, E.W. Meineke, Chem. Ber. 105 (1972)
2558.
[33] (a) L. Maier, in: G.M. Kosolapoff, L. Maier (Eds.), Organic Phosphorus
Compounds, Wiley-Interscience, New York, 1972, p. 339;
(b) H.R. Hudson, in: F.R. Hartley (Ed.), The Chemistry of Organic Phosphorus
Compounds, John Wiley & Sons, New York, 1990;
(c) L.D. Quin, A Guide to Organophosphorus Chemistry, John Wiley & Sons,
New York, 2000.
References
[1] (a) J.D. Atwood, Inorganic and Organometallic Reaction Mechanisms, second
ed., Wiley-VCH, New York, 1997;
(b) D.J. Darensbourg, Adv. Organomet. Chem. 21 (1982) 113.
[2] M.J. Wovkulich, J.D. Atwood, J. Organomet. Chem. 184 (1980) 77.
[3] (a) R.L. Keiter, L.W. Cary, J. Am. Chem. Soc. 94 (1972) 9232;
(b) J.A. Connor, J.P. Day, E.M. Jones, G.K. McEwen, J. Chem. Soc. Dalton Trans.
(1973) 347;
[34] (a) W. Uedelhoven, D. Neugebauer, F.R. Kreissl, J. Organomet. Chem. 217
(1981) 183;
(b) A.E. Bruce, A.S. Gamble, T.L. Tonker, J.L. Templeton, Organometallics 6
(1987) 1350.