The interaction of chlorides of V, Cr, Mo, and W with the lithium or Grignard reagents derived from chloromethyltrimethylsilane produces thermally stable alkyls of formula V(CH2SiMe3)4, VO(CH2SiMe3)3, Cr(CH2SiMe3)4, and M2(CH2SiMe3)6(M = Mo or W). The compounds have been investigated, where feasible, by i.r., Raman, electronic, e.s.r., and n.m.r. spectroscopy and the various spectral assignments are discussed in terms of proposed structures for the compounds.