Metallocene derivatives of early transition metals. Part 4. Chemistry of the complexes [M(η-C ₅ H ₅ ) ₂ RR′][M = Ti, Zr, or Hf; R = CH ₂ M′Me ₃ (M′= C, Si, Ge, or Sn) or CH(SiMe ₃ ) ₂ ; R′= Cl or alkyl] and the X-ray structures of [Zr(η-C ₅ H ₅ ) ₂ (CH ₂ M′Me ₃ ) ₂ ](M′= C or Si)

The metallocene(IV) halogeno-alkyls [M(η-C5H5)2RX][type (i) R = CH2SnMe3, X = Cl or Br, M = Ti (also X = I), Zr, or Hf; type (ii) R = CH2SiMe3, X = Cl or Br, M = Ti, Zr, or Hf; type (iii) R = CH2GeMe3, X = Cl, M = Ti] have been prepared either by interaction of the appropriate Grignard reagent and [M(η-C5H5)2Cl2] or from [M(η-C5H5)2RCl] and Mg(CH2SnMe3)X (Cl–X exchange). Metallocene(IV) dialkyls [M(η-C5H5)2RR′][type (iv) R = CH2SnMe3= R′, M = Ti, Zr, or Hf; type (v) R = CH2SnMe3, R′= CH2SiMe3, M = Ti, Zr, or Hf; type (vi) R = CH2CMe3= R′, M = Ti or Zr; type (vii) R = CH2SnMe3; R′= CH2CMe3, CH2GeMe3, or Me; M = Ti; type(viii) R = CH2SiMe3, R′= CH2GeMe3, M = Ti; type (ix) R = CH(SiMe3)2; R′= Me, Et, Prn, CH2SiMe3, or Ph; M = Zr] have been synthesised by reaction of (a)[for type (v)][M(η-C5H5)2] with 2Mg(CH2SnMe3)X (X = Cl or Br) or (b)[M(η-C5H5)2RX] with LiR′. Also obtained are [Ti(η-C5H5)2Cl(OCH2SiMe3)] and [{Zr(η-C5H5)2[CH(SiMe3)2]H}2], the latter from [Zr(η-C5H5)2{CH(SiMe3)2}Cl] and Li[AlH4] or [Zr(η-C5H5)2Cl2] and successively Li[AlH(OBut)3] and Li[CH(SiMe3)2]. The reaction of an equimolar portion of HCl in OEt2 and [Ti(C5H5)2(CH2SnMe3)Cl] gives predominantly the products of CH2–SnMe3, rather than Ti–CH2, scission. By contrast, the dialkyls [M(η-C5H5)2RR′], containing one or two CH2SnMe3 ligands, give largely RH or R′H and [M(η-C5H5)2Cl (R′ or R)]; the relative ability of R as a leaving group decreases in the sequence CH2SnMe3 > CH2CMe3 > CH2SiMe3 CH2GeMe3 > CH3, the distinctions being more marked for Ti than Zr or Hf. The dialkyls are generally stable when heated at 80 °C in PhMe, except for the titanium complexes; [Ti(η-C5H5)2(CH2M′Me3)2](M′= Si or Ge) gives M′Me4 as the sole volatile product, with t½ 110 (M′= Si) or 140 min (M′= Sn). Treatment of [Zr(η-C5H5)2RX][type (ix)] in C6H6 with CO under ambient conditions affords the appropriate η2-acyl [Zr(η-C5H5)2(η2-COR)X][type (x), R = CH2CMe3 or CH2SiMe3, X = Cl or R; or type (xi), R = CH(SiMe3)2, X = Me]; the formation of type (xi), rather than the isomer resulting from CO insertion into the less hindered Zr–Me bond, is noteworthy. A single-crystal X-ray diffraction study has been carried out on [Zr(η-C5H5)2(CH2M′Me3)2][M′= C, (28) or Si, (42)]. Crystals of complex (28) are tetragonal, space group I, with a= 9.142(4), b= 9.142(4), c= 23.326(9)Å, β= 90°, and Z= 4. Crystals of (42) are monoclinic, space group P21/n, a= 13.745(6), b= 7.048(3), c= 22.057(9)Å, β= 95.65(4)°, and Z= 4. For complex (28), 487 reflections have been considered and the data refined to R= 0.029, R′= 0.032; for complex (42), 2 688 independent reflections led to R= 0.029, R′= 0.033. The slightly larger steric requirement of the neopentyl ligand compared with –CH2SiMe3 manifests itself in a larger Zr–cyclopentadienyl approach but the Zr–CH2 bond length is indistinguishable, 2.51 (2)Å for (28) and 2.52(2)Å for (42).