2 Homometallic Alkoxides

Zr⊲CH2Bu t ⊳4 C 4RfOH benzene
! Zr⊲ORf⊳4 C 4CMe4
where Rf D CH⊲CF3⊳2, C⊲CF3⊳Me2, C⊲CF3⊳2Me, C⊲CF3⊳3. 398,398a
V(C6H2Me3-
2,4,6) 3(thf)
HOCMe 2 CH 2 OMe
toluene, (−THF),
(−3HOC 6 H 2 Me 3 -2,4,6)
+3ButOH toluene, (−THF),
(−3HOC6H2Me3-2,4,6) where R D Me, Et, Pr i ,CH2Bu t . 400
V(OCMe 2CH 2OMe) 3 340
1
2
Homometallic Alkoxides 47
⊲2.132⊳
(2.133)
(Bu t O) 2V(m-O)(m-OBu t )V(OBu t ) 2 399 (2.134)
Cr⊲C5H5⊳2 C 2ROH ! 1
n [Cr⊲OR⊳2]n C 2C5H6
⊲Me3P⊳3RhMe C ROH toluene
! ⊲Me3P⊳3RhOR C CH4
where R D CH2CF3, CH(CF3⊳2. 401
CHOCH⊲CF3⊳2
CPPh3
!⊲Ph3P⊳3Cu[OCH⊲CF3⊳2] C CH4
⊲2.135⊳
⊲2.136⊳
(2.137)
CHOCHPh2
⊲Ph3P⊳2CuMe⊲OEt2⊳0.5 402 !⊲Ph3P⊳2Cu⊲OCHPh2⊳ C CH4 (2.138)
CHOCHPh2 !⊲Ph3P⊳3Cu⊲OCHPh2⊳ C CH4 (2.139)
CPPh3
Reactions of alcohols ROH, with CoMe⊲PMe3⊳4 afford polymers of the formula
[Co⊲OR⊳2]n (Eq. 2.140). 403
2CoMe⊲PMe3⊳4 C 2ROH ! 1
n [Co⊲OR⊳2]n C Co⊲PMe3⊳4 C 4PMe3 C 2CH4
⊲2.140⊳
where R D Me, Et, Ph, SiMe3.
Interactions of ⊲bpy⊳NiR2 404 with HOCH⊲CF3⊳2 and AlEt3 405 with HOCH2CCl3 give
corresponding alkoxide derivatives:
⊲bpy⊳NiR2 C 2HOCH⊲CF3⊳2 ! ⊲bpy⊳Nif⊲OCH⊲CF3⊳2g2 C 2RH ⊲2.141⊳
AlEt3 C 3HOCH2CCl3 ! Al⊲OCH2CCl3⊳3 C 3C2H6 ⊲2.142⊳