2 Homometallic Alkoxides

4Mo2(OPr i )6 + 18CO
(excess)
Homometallic Alkoxides 151
Pri OPri O
Mo Mo
O
Pri Pr CO
CO
iO Pri 2Mo(CO)6 + 3 (2.358)
O
OPr i
OPr i
OPr i
OPr i
4W2(OPri Pr
)6 24CO 2W(CO)6 3 W
i
O
O
Pr
W
i
Pr CO
CO
iO PriO OPri CO
+ +
CO
(2.359)
Treatment of W2⊲OPr i ⊳6⊲py⊳2 with two molar equivalents of CO in toluene led
to the isolation of two products: W2⊲OPr i ⊳6⊲CO⊳4 1033 and [⊲Pr i O⊳3W⊲ -CO⊳⊲ -
OPr i ⊳W⊲OPr i ⊳2py]2, 1035 which have been characterized by X-ray crystallography.
Reactions of CO with M2⊲OR⊳6 (M D Mo, W; R D Pr i ,CH2Bu t ) compounds in
hydrocarbon solvents at 25 Ž C and 1 atm pressure in the presence of donor ligands
(C5H5N⊲py⊳, HNMe2), lead to the formation of M2⊲OR⊳6⊲L⊳2⊲ -CO⊳ products, which
have been structurally characterized 1036 for M D Mo, R D Pr i and L D pyridine:
M2(OR) 6 + CO + 2L
hydrocarbon
25 °C,1 atm
RO
O
C OR
RO
Py
M
R
O
M
OR
Py
O
R
(2.360)
4.17.1.3 Reactions with nitric oxide
Hydrocarbon solutions of Mo2⊲OR⊳6 compounds react readily, irreversibly, and apparently
quantitatively with NO at room temperature to yield Mo2⊲OR⊳6⊲NO⊳2 according
to Eq. (2.361): 1037,1038
Mo 2(OR)6
+ 2NO
where R D CH2Bu t ,CHMe2, CMe3, Pr i .
NO
RO Mo
OR
R
O
O
R
Me2NH RO
Mo
R
O
ON
OR
O
R
OR
Mo
NO
+ 2Me 2NH
OR
Mo
NHMe 2
OR
NO
OR
(2.361)