Prospects for dinuclear transition metal chemistry illustrated by recent advances in the chemistry of dimolybdenum and ditungsten

The term classical coordination complex refers to a Werner type complex. See F. A. Cotton and G. Wilkinson inAdvanced Inorganic Chemistry 3rd Edit., Interscience, 1972, Ch. 21. F. A. Cotton,Chem. Soc. Rev., 4, 27 (1975). F. A. Cotton,Acc. Chem. Res., 11, 225 (1978). W. C. Trogler and H. B. Gray,Acc. Chem. Res., 11, 232 (1978). F. A. Cotton and J. V. Brencic,Inorg. Chem., 8, 7 (1969). F. A. Cotton, J. M. Troup, H. R. Webb, D. H. Williamson and G. Wilkinson,J. Am. Chern. Soc., 96, 3824 (1974). F. A. Cotton, Z. C. Mester and T. R. Webb,Acta Crystallogr., 308, 2768 (1974). F. A. Cotton, T. Inglis, M. Kilner and T. R. Webb,Inorg. Chem., 15, 2023 (1975). L. Richard, P. Karagiannidis and R. Weiss,Inorg. Chem., 12, 2179 (1973). F. A. Cotton, S. Koch and M. Miller,J. Am. Chem. Soc., 99, 7372 (1977). The shortest of all known metal-metal bonds is found in Li6Cr2(o-C6H4O)4Br2.6Et2O [Cr-Cr = 1.830(4) Å] which contains the o-oxyphenyl ligand. The Cr-Cr distance in Cr2 (DMP)4 is only slightly longer at 1.847(1). Å See F. A. Cotton and S. Koch,Inorg. Chem.,17, 2021 (1978). F. A. Cotton,Science, 145, 1305 (1964). F. A. Cotton,Inorg. Chern., 4, 334 (1965). J. G. Norman Jr. and H. J. Kolari,J. Chem. Soc. Cbem. Commun., 649 (1974). J. G. Norman Jr. and H. J. Kolari,J. Am. Chem. Soc., 97, 33 (1975). F. A. Cotton and B. J. Kalbacher,Inorg. Chem., 16, 2386 (1977). J. G. Norman Jr. and H. J. Kolari,J. Am. Chem. Soc., 100, 791 (1978). D. M. Collins, F. A. Cotton, S. Koch, M. Millar and C. A. Murillo,J. Am. Chem. Soc., 99, 1259 (1977). F. A. Cotton, S. Koch, K. Mertis, M. Millar and G. Wilkinson,J. Am. Chem. Soc., 99, 4989 (1977). F. A. Cotton and M. Jeremic,Syn. Inorg. Metal. Chem., 1, 265 (1971). T. Stephenson and D. Whittaker,Inorg. Nucl. Chem. Lett., 5, 569 (1969). A. Bino, F. A. Cotton, Z. Dori, S. Koch, H. Kippers, M. Miller and J. C. Sekutowski,Inorg. Chem., 17, 3245 (1978). Related reactions involving MO(CO)6 and RCO2H have yielded Mo2(O2CR)4 compounds. See ref. 4. W. H. DeRoode, K. Vrieze, E. A. Keener von Gustorf and A. Ritter,J. Organometal. Chem., 135, 183 (1977). W. H. DeRoode and K. Vrieze,J. Organometal. Chem., 145, 207 (1978). T. Aoki, A. Furusaki, Y. Tomice, K. Ono and K. Taraka,Bull. Chem. Soc. Japan, 42, 545 (1969). F. A. Cotton and J. R. Pipal,J. Am. Chem. Soc., 93, 5441 (1971). F. A. Cotton and M. W. Extine,J. Am. Chem. Soc., 100, 3788 (1978). F. A. Cotton and S. Koch,J. Am. Chem. Soc., 99, 7371 (1977). J. G. Norman Jr., H. J. Kolari, H. B. Gray and W. C. Trogler,Inorg. Chem., 16, 987 (1977). W. Klotzbücher and G. A. Ozin,Inorg. Chem., 16, 984 (1977). M. H. Chisholm and F. A. Cotton,Acc. Chem. Res., 11, 356 (1978). F. Huq, W. Mowat, A. Shortland, A. C. Skapski and G. Wilkinson,J. Chem. Soc. Chem. Commun., 1079 (1971). W. Mowat, A. J. Shortland, G. Yagupsky, N. J. Hill and G. Wilkinson,J. Chem. Soc. Dalton Trans., 533 (1972). M. H. Chisholm and W. W. Reichert,J. Am. Chem. Soc., 96, 1249 (1974). M. H. Chisholm, F. A. Cotton, B. A. Frenz, W. W. Reichert, L. W. Shive and B. R. Stults,J. Am. Chem. Soc., 98, 4469 (1976). M. H. Chisholm, M. W. Extine and W. Reichert,Advan. in Chem. Ser., 150, 273 (1976). M. H. Chisholm, F. A. Cotton, C. A. Murillo and W. W. Reichert,J. Am. Chem. Soc., 99, 1652 (1977). M. H. Chisholm, F. A. Cotton, C. A. Murillo and W. W. Reichert,Inorg. Chem., 16, 1801 (1977). For a discussion of N-to-M π-bonding in transition metal dialkylamides see D. C. Bradley and M, H. Chisholm,Acc. Chem. Res., 9, 273 (1976). M. H. Chisholm, F. A. Cotton, M. W. Extine and W. W. Reichert,J. Am. Chem. Soc., 100, 153 (1978). M. H. Chisholm, F. A. Cotton, M. W. Extine and W. W. Reichert,J. Am. Chem. Soc., 100, 1727 (1978). M. H. Chisholm, F. A. Cotton, M. W. Extine and B. R. Stults,Inorg. Chem., 16, 603 (1977). F. A. Cotton, G. G. Stanley, B. Kalbacher, J. C. Green, E. Seddon and M. H. Chisholm,Proc. Natl. Acad. Sci., USA, 74, 3109 (1977). J. Potenza, P. Giordano, D. Mastropaolo, A. Efraty and R. B. King,J. Chem. Soc. Chem. Commun., 1333 (1972). R. J. Klingler, W. Butler and M. D. Curtis,J. Am. Chem. Soc., 97, 3535 (1975); ibid,100, 5034 (1978). R. D. Adams, D. M. Collins and F. A. Cotton,Inorg. Chem., 13, 1086 (1974). This is true for all the transition elements. The P2Pt-PtP2 compound, where P2 = t-Bu2P(CH2)3PBu-t2, which has an unbridged Pt-Pt bond is a good candidate for a M-M double bond. However, the long Pt-Pt distance, 2.76(1) A, and calculations suggest the presence of a single order M-M bond. See T. Yoshida, T. Yamagata T. H. Tulip, J. A. Ibers and S. Otsuka, J. Am. Chem. Soc., 100, 2063 (1978), and A. Dedien and R. Hoffmann, ibid, 100, 2074 (1978). M. H. Chisholm, F. A. Cotton, M. W. Extine and R. L. Kelly,J. Am. Chem. Soc., 100, 2556 (1978). M. H. Chisholm, F. A. Cotton, M. W. Extine and R. L. Kelly,Inorg. Chem., 17, 2944 (1978). F. A. Cotton,J. Less. Common Mets., 54, 3 (1977). M. H. Chisholm, F. A. Cotton, M. W. Extine and R. L. Kelly,J. Am. Chem. Soc., 100, 3354 (1978). For a review of metal nitrosyl chemistry, see R. Eisenberg and C. D. Meyer,Ace. Chem. Res., 8, 26 (1975). C. F. Putnik, J. J. Welter, G. D. Stucky, M. J. D'Aniello, B. A. Sosinsky, J. F. Kirner and E. L. Muetterties,J. Am. Chem. Soc., 100, 4107 (1978). Dr. D. G. Garner, personal communication. F. A. Cotton and C. G. Harris,Inorg. Chem., 6, 924 (1967). G. L. Geoffroy, H. B. Gray and G. S. Hammond,J. Am. Chem. Soc., 96, 5565 (1974). J. A. Connor, G. Pilcher, H. A. Skinner, M. H. Chisholm and F. A. Cotton,J. Am. Chem. Soc., 100,7738 (1978). See ref. 4 and references therein and J. L. Templeton, Chem.Soc. Rev., in press. J. S. San Filippo Jr.,Inorg. Chem., 11, 3140 (1972). R. A. Andersen, R. A. Jones and G. Wilkinson,J. Chem. Soc. Dalton Trans., 446 (1978). K. Mislow,Acc. Chem. Res., 10, 26 (1977). For a discussion of the magnetic shielding of the M=M bond see ref. 32. M. H. Chisholm, F. A. Cotton, M. W. Extine, M. Millar and B. R. Stults,Inorg. Chem., 15, 2244 (1976). M. H. Chisholm, D. A. Haitko and C. A. Murillo,J. Am. Chem. Soc., 100, 6262 (1978). M. H. Chisholm, F. A. Cotton, M. W. Extine, M. Millar and B. R. Stults,Inorg. Chem., 16, 320 (1976). J. Albright and R. Hoffmann, personal communication. M. H. Chisholm, M. W. Extine, R. L. Kelly, W. C. Mills, C. A. Murillo, L. A. Rankel and W. W. Reichert,Inorg. Chem., 17, 1673 (1978). M. H. Chisholm and M. W. Extine,J. Am. Chem. Soc., 98, 6393 (1976). T. G. Appleton, H. C. Clark and L. E. Manzer,Coord. Chem. Rev., 10, 335 (1973). M. H. Chisholm and F. A. Cotton, to be published. A. Wojcicki,Adv. Organometal. Chem., 11, 87 (1973); ibid,12, 31 (1974). D. C. Bradley and K. Fisher,M.T.Y. Int. Rev. Sci., Ser. One, 5, 65 (1972); D. C. Bradley,Adv. Inorg. Chem. Radiochem., 15, 259 (1972). M. H. Chisholm and M. W. Extine,J. Am. Chem. Soc., 99, 782, 792 (1977). Labelling studies are currently in progress to determine whether this is an intermolecular or intermolecular process. M. H. Chisholm and R. L. Kelly, to be published. F. A. Cotton and B. J. Kalbaeher,Inorg. Chem., 15, 522 (1976). F. A. Cotton, M. W. Extine and R. H. Niswander,Inorg. Chem., 17, 692 (1978). L. Ricard, J. Estienne and R. Weiss,Inorg. Chem., 12, 2182 (1973). W. I. Bailey, M. H. Chisholm, F. A. Cotton and L. A. Rankel,J. Am. Chem. Soc., 100, 5764 (1978). W. I. Bailey, M. H. Chisholm, F. A. Cotton, C. A. Murillo and L. A. Rankel,J. Am. Chem. Soc., 100, 802 (1978). M. H. Chisholm, F. A. Cotton, M. W. Extine and L. A. Rankel,J. Am. Cbern. Soc., 100, 807 (1978). S. A. R. Knox, R. F. D. Stansfield, F. G. A. Stone, M. J. Winter and P. Woodward,J. Chem. Soc. Chem. Commun., 221 (1978). M, H, Chisholm, Advan. in Chem. Ser., in press. The reaction between the permethylated analogue (Me5C5)2Mo2(CO)4 and 2 NO was first noted: R. B. King, A. Efratey and W. M. Douglas,J. Organometal. Chem., 60, 125 (1973). M. H. Chisholm, F. A. Cotton, M. W. Extine and R. L. Kelly,Inorg. Chem., 18, in press (1979). M. Akiyama, M. H. Chisholm, F. A. Cotton, M. W. Extine and C. A. Murillo,Inorg. Chem., 16, 2407 (1977). M. Akiyama, M. H. Chisholm, F. A. Cotton, M. W. Extine and D. Little, to be published. R. N. McGinnis, T. R. Ryan and R. E. McCarley,J. Am. Chem. Soc., 100, 7900 (1978). V. Katovic and R. E. McCarley,J. Am. Chem. Soc., 100, 5586 (1978). R. A. Andersen, R. A. Jones and G. Wilkinson,J. Chem. Soc., Dalton Trans., 446 (1978).