Oxidation of fac-[M(CO) 3(NCMe) 3] (M=Mo or W) with I 2Cl 6. Reactions of the seven-coordinate complex [WCl(ClICl)(CO) 3(NCMe) 2]
Reaction of fac-[Mo(CO) 3(NCMe) 3] (prepared in situ) with I 2Cl 6 resulted in a large amount of effervescence and the formation of a dark red–brown solution, and a yellow precipitate. Both the yellow precipitate and the orange solid resulting from work-up of the dark red–brown solution were found t...
Saved in:
Published in | Polyhedron Vol. 20; no. 19; pp. 2559 - 2566 |
---|---|
Main Authors | , |
Format | Journal Article |
Language | English |
Published |
Elsevier Ltd
2001
|
Subjects | |
Online Access | Get full text |
Cover
Loading…
Summary: | Reaction of
fac-[Mo(CO)
3(NCMe)
3] (prepared in situ) with I
2Cl
6 resulted in a large amount of effervescence and the formation of a dark red–brown solution, and a yellow precipitate. Both the yellow precipitate and the orange solid resulting from work-up of the dark red–brown solution were found to be the MoMo bonded non-carbonyl containing tetracationic complex [Mo
2(NCMe)
8][Cl]
2[ClICl]
2 (
1). Oxidation of
fac-[W(CO)
3(NCMe)
3] (prepared in situ) with I
2Cl
6 gave the seven-coordinate complex [WCl(ClICl)(CO)
3(NCMe)
2] (
2). Treatment of
2 with an equimolar amount of L {L=PPh
3 [stirred for 1 min], AsPh
3 [stirred for 3 min] and SbPh
3 [stirred for 5 min]} in CH
2Cl
2 at room temperature gave [WCl(ClICl)(CO)
3(NCMe)L] (
3–
5). Reaction of [WCl(ClICl)(CO)
3(NCMe)
2] with an equimolar amount of L {L=PPh
3, AsPh
3 and SbPh
3} in CH
2Cl
2 at room temperature for 24 h gave the chloro-bridged complexes [{W(μ-Cl)(ClICl)(CO)
3L}
2] (
6–
8). Reaction of [WCl(ClICl)(CO)
3(NCMe)
2] with 2 equiv. of RC
2R (R=Me or Ph) in CH
2Cl
2 at room temperature gave the bis(alkyne) complexes [WCl(ClICl)(CO)(NCMe)(η
2-RC
2R)
2] (
9 and
10). The reactions of [WCl(ClICl)(CO)(NCMe)(η
2-PhC
2Ph)
2] with 1 equiv. of L
∧L {L
∧L=Ph
2P(CH
2)
n
PPh
2 (
n=1–4, 6) or 2,2′-bipyridine} in CH
2Cl
2 at room temperature afforded the complexes [WCl(ClICl)(CO)(L
∧L)(η
2-PhC
2Ph)] (
11–
16). Treatment of [WCl(ClICl)(CO)(NCMe)(η
2-RC
2R)
2] (R=Me or Ph) with 2 equiv. of L
∧L {L
∧L=Ph
2P(CH
2)
n
PPh
2 (
n=1–4, 6) in CH
2Cl
2 at room temperature afforded the dicationic complexes [W(CO)(L
∧L)
2(η
2-RC
2R)][Cl][ClICl]·CH
2Cl
2 (
17–
26). All the new complexes described in this paper were characterised by elemental analysis, IR and
1H NMR spectroscopy.
Oxidation of
fac-[M(CO)
3(NCMe)
3] (prepared in situ) with I
2Cl
6 gives the metal–metal bonded complex [Mo
2(NCMe)
8][Cl]
2[ClICl]
2, and the seven-coordinate complex [WCl(ClICl)(CO)
3(NCMe)
2]. The reactions of [WCl(ClICl)(CO)
3(NCMe)
2] with both neutral donor ligands and alkynes is described. The chemistry of the bis(alkyne) complexes [WCl(ClICl)(CO)(NCMe)(η
2-RC
2R)
2] (R=Me or Ph) is also discussed. |
---|---|
ISSN: | 0277-5387 |
DOI: | 10.1016/S0277-5387(01)00853-1 |