2 Homometallic Alkoxides

Table 6.3 W–OAr distances for various aryloxide derivatives of tungsten
Metal Aryloxides 471
Coordination Electron Bond length ( ˚A)
Compound number count M–OAr Ref.
[W⊲OC6H5⊳⊲H⊳3⊲PMe3⊳4] 8 18 2.129 (8) i
[NEt4][W⊲OC6H3Ph2-2,6⊳⊲CO⊳5] 6 18 2.165 (9), 2.175 (9) ii
[NEt4][W⊲OC6H5⊳⊲CO⊳4⊲PMePh2⊳] 6 18 2.191 (6) ii
[NEt4][W⊲OC6H5⊳⊲CO⊳5] 6 18 2.182 (19), 2.205 (21) iii
[W⊲O- 1 -C6H4⊳⊲H⊳2⊲PMe3⊳4] 8 18 2.177 (5) iv, v
[W⊲OC6H3Me-CH2⊳⊲H⊳2⊲PMe3⊳4] 8 18 2.145 (8) v
[W⊲OC6H3Ph- 6 -C6H5⊳⊲H⊳⊲PMePh2⊳2] Ł 18 2.163 (9) vi
[W⊲OC6H3Ph- 6- C6H5⊳⊲Cl⊳⊲PMePh2⊳2]
Ł 18 2.128 (4) vi
[⊲Cp Ł ⊳W(OAr)⊲C2Me2⊳2] Ł 16/18 2.072 (7) vii
[W⊲OC6H3Ph- 6-C6H5⊳⊲OAr⊳⊲PMePh2⊳] Ł 16 2.001 (6), 2.033 (6) viii, ix
[W⊲OC6H3Ph- 6-C6H5⊳⊲OAr⊳⊲dppm⊳] Ł 16 2.038 (5), 1.986 (5) viii, ix
all-trans-[W⊲OC6H3Ph2-
6 14 1.966 (4) x
2,6⊳2Cl2⊲PMe2Ph⊳2]
all-trans-[W⊲OC6H4Me-
6 14 1.848 (5), 1.840 (5) xi
4⊳2Cl2⊲PMePh2⊳2]
[W⊲OC6H3Ph- 1-C6H4⊳2⊲PMe2Ph⊳2] 6 14 1.88 (1), 1.87 (1) viii, ix
trans-[W⊲OC6H3Ph2-2,6⊳2Cl3⊲THF⊳] 6 13 1.855 (5), 1.857 (5) x
[W⊲OC6H2Cl3-2,4,6⊳4Cl⊲OEt2⊳] 6 13 1.853 (9), 1.964 (10) xii
cis-[W⊲OC6H3Ph2-2,6⊳2Cl4] 6 12 1.851 (3), 1.840 (3) x
cis-[W⊲OC6H3Pri 2-2,6⊳2Cl4] 6 12 1.814 (8), 1.797 (9) xiii
Ł Undefined number.
i K.W. Chiu, R.A. Jones, G. Wilkinson, A.M.R. Galas, M.B. Hursthouse, and K.M.A. Malik, J.
Chem. Soc., Dalton Trans., 1204 (1981).
ii D.J. Darensbourg, B.L. Mueller, C.J. Bischoff, S.S. Chojnacki, and J.H. Reibenspies, Inorg.
Chem., 30, 2418 (1991).
iii D.J. Darensbourg, K.M. Sanchez, J.H. Reibenspies, and A.L. Rheingold, J. Am. Chem. Soc.,
111, 7094 (1989).
iv D. Rabinovich, R. Zelman, and G. Parkin, J. Am. Chem. Soc., 112, 9632 (1990).
v D. Rabinovich, R. Zelman, and G. Parkin, J. Am. Chem. Soc., 114, 4611 (1992).
vi J.L. Kerschner, E.M. Torres, P.E. Fanwick, I.P. Rothwell, and J.C. Huffman, Organometallics,
8, 1424 (1989).
vii M.B. O’Regan, M.G. Vale, J.F. Payack, and R.R. Schrock, Inorg. Chem., 31, 1112 (1992).
viii J.L. Kerschner, I.P. Rothwell, J.C. Huffman, and W.E. Streib, Organometallics, 7, 1871
(1988).
ix J.L. Kerschner, P.E. Fanwick, I.P. Rothwell, and J.C. Huffman, Organometallics, 8, 1431
(1989).
x J.L. Kerschner, P.E. Fanwick, I.P. Rothwell, and J.C. Huffman, Inorg. Chem., 28, 780
(1989).
xi L.M. Atagi and J.M. Mayer, Angew. Chem., Int. Ed. Engl., 32, 439 (1993).
xii R.M. Kolodziej, R.R. Schrock, and J.C. Dewan, Inorg. Chem., 28, 1243 (1989).
xiii H. Yasuda, Y. Nakayama, K. Takei, A. Nakamura, Y. Kai, and N. Kanehisa, J. Organomet.
Chem., 473, 105 (1994).
in the range 2.13–2.20 ˚A. As the formal electron count at the tungsten metal centre
decreases so there is a dramatic decrease in the W–OAr bond length reaching a value
of 1.786 (9) ˚A for one of the ligands in the compound cis-[W(OC6H3Pr i 2 -2,6)2Cl4].
ThedropinW–O(aryloxide) distance of >0.3 ˚A is comparable to that found for the
group 5 metals above.