TY - JOUR
T1 - Synthesis and Reactivity of A Neutral Tungsten(o) Alkyl Complex
T2 - Insertion of C0
2
into The W-ch
3
bond of Trans,trans-w(ch
3
)(co)2(no)(pph3)2 and The Structural Characterization of Trans-w(η
2
-02cch
3
)(c0)(n0)(pph
3
)
2
AU - Holl, Mark M.
AU - Hillhouse, Gregory L.
AU - Folting, Kirsten
AU - Huffman, John C.
PY - 1987/7/1
Y1 - 1987/7/1
N2 -
Reaction of trans,trans-WCl(CO)
2
(NO)(PPh
3
)2 (1) with CH
3
Li or (CH
3
)
2
Zn affords trans,trans-W-(CH
3
HCO)
2
(NO)(PPh
3
)
2
(2) in good yields. Treatment of 2 with DC1 gives 1 and CH
3
D quantitatively. Reaction of 2 with carbon monoxide (2 atm, 80 °C) results in a reversible substitution of CO for PPh
3
to give mer-W(CH
3
)(CO)
3
(NO)(PPh
3
) (3). Carbon dioxide undergoes a 1,2-insertion reaction with 2 to give the monodentate acetate complex trans,trans-W[η
1
-0C(0)CH
3
](C0)
2
(N0)(PPh
3
)
2
(4), which reversibly loses CO on heating to yield the bidentate acetate derivative trans-W(η
2
-0
2
CCH
3
)(C0)(N0)(PPh
3
)
2
(5). Monoclinic prisms of 5 were grown from a dichloromethane/benzene solution and crystallized in space group P2
1
/a with Z = 4, a = 20.864 (5) A, b = 9.729 (2) A, c = 17.504 (4) A, and β = 103.21 (1)°. An X-ray diffraction study at -91 ± 3 °C showed that the acetate ligand is bound in an asymmetric fashion to the tungsten center and that the nitrosyl and carbonyl ligands are not substantially disordered. Salient metrical parameters of the structure include the following: W(l)-0(4) == 2.249 (5) A, W(l)-0(5) = 2.217 (5) A, 0(4)-C(6) = 1.270 (10) A, 0(5)-C(6) = 1.302 (10) A, W(l)-C(8) = 1.914 (8) A, C(8)-0(9) = 1.171 (9) A, W(l)-N(10) = 1.836 (7) A, N(10)-O(ll) = 1.203 (9) A, and W(l)-N(10)-O(ll) = 178.3 (6)°. The least-squares refinement converged to R(F) = 0.036 and R
w
(F) = 0.036 for 3518 unique data with F > 3σ(F).
AB -
Reaction of trans,trans-WCl(CO)
2
(NO)(PPh
3
)2 (1) with CH
3
Li or (CH
3
)
2
Zn affords trans,trans-W-(CH
3
HCO)
2
(NO)(PPh
3
)
2
(2) in good yields. Treatment of 2 with DC1 gives 1 and CH
3
D quantitatively. Reaction of 2 with carbon monoxide (2 atm, 80 °C) results in a reversible substitution of CO for PPh
3
to give mer-W(CH
3
)(CO)
3
(NO)(PPh
3
) (3). Carbon dioxide undergoes a 1,2-insertion reaction with 2 to give the monodentate acetate complex trans,trans-W[η
1
-0C(0)CH
3
](C0)
2
(N0)(PPh
3
)
2
(4), which reversibly loses CO on heating to yield the bidentate acetate derivative trans-W(η
2
-0
2
CCH
3
)(C0)(N0)(PPh
3
)
2
(5). Monoclinic prisms of 5 were grown from a dichloromethane/benzene solution and crystallized in space group P2
1
/a with Z = 4, a = 20.864 (5) A, b = 9.729 (2) A, c = 17.504 (4) A, and β = 103.21 (1)°. An X-ray diffraction study at -91 ± 3 °C showed that the acetate ligand is bound in an asymmetric fashion to the tungsten center and that the nitrosyl and carbonyl ligands are not substantially disordered. Salient metrical parameters of the structure include the following: W(l)-0(4) == 2.249 (5) A, W(l)-0(5) = 2.217 (5) A, 0(4)-C(6) = 1.270 (10) A, 0(5)-C(6) = 1.302 (10) A, W(l)-C(8) = 1.914 (8) A, C(8)-0(9) = 1.171 (9) A, W(l)-N(10) = 1.836 (7) A, N(10)-O(ll) = 1.203 (9) A, and W(l)-N(10)-O(ll) = 178.3 (6)°. The least-squares refinement converged to R(F) = 0.036 and R
w
(F) = 0.036 for 3518 unique data with F > 3σ(F).
UR - http://www.scopus.com/inward/record.url?scp=0000304530&partnerID=8YFLogxK
U2 - 10.1021/om00150a026
DO - 10.1021/om00150a026
M3 - Article
AN - SCOPUS:0000304530
VL - 6
SP - 1522
EP - 1527
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 7
ER -