2 Homometallic Alkoxides

Metal Aryloxides 621
Table 6.39 (Continued)
Bond Bond
length ( ˚A) angle ( Ž )
Compound Aryloxide M–O M–O–Ar Ref.
[Ni2⊲ -
OAr⊳2⊲DMF⊳2⊲OH2⊳2][BPh4]2.4DMF
2-OC6H4⊲20 edge-shared bis-octahedron,
-
bipy)-2
1.993 (4),
2.121 (4)
xv
axial OH2
[Ni2⊲ -OAr⊳2⊲DMF⊳6][BPh4]2.2Et2O 2-OC6H4⊲20 edge-shared bis-octahedron, axial py
-
py)-2
2.003 (3),
2.051 (3)
xvi
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accounts for its reaction with electrophiles such as CO2 to generate insertion products
(Section 5.2). Hence treatment of trans-[NiMe2(PMe3)2] ortrans-[PdR2(PR3)2]
(R D Me, Et) with para-substituted phenols yields the corresponding compounds trans-
[MMe(OAr)(HOAr)(PR3)2](MD Ni, Pd). 489 Both compounds for R D Me, Ar D Ph as
well as the non-phenol adduct of Pd were crystallographically characterized. In the case
of cis-[PtMe2(PMe3)2] initial conversion to cis-[PtMefOCH⊲CF3⊳2g⊲PMe3⊳2] followed
by addition of phenol led to the simple phenoxide cis-[Pt(OPh)Me(PMe3)2] priorto
formation of the phenol adduct. 240 The one-electron oxidation of [PdMe(OPh)(dmpe)]
results in cleavage of the Pd–OPh bond. 490
Other related alkyl substrates include [PtMe2(bipy)], 491
[PdMe2(NMe2CH2C6H4PPh2)], 492 and [PdMe2(TMEDA)] 493 which all form mono-aryloxides.
The product [Pt(OPh)Me(bipy)] reacts with MeI to form [Pt(OPh)(I)Me2(bipy)]