Studies with the Ruthenacarborane Complex [Ru(CO)(PPh3)(THF)(5-7,8-C2B9H11)]: R
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- 作者：Shaowu Du ; Dianne D. Ellis ; Paul A. Jelliss ; Jason A. Kautz ; John M. Malget ; and F. Gordon A. Stone
- 刊名：Organometallics
- 出版年：2000
- 出版时间：May 15, 2000
- 年：2000
- 卷：19
- 期：10
- 页码：1983 - 1992
- 全文大小：178K
- 年卷期：v.19,no.10(May 15, 2000)
- ISSN：1520-6041
文摘
The syntheses of the complexes [Y][RuX(L)(PPh3)(
5-7,8-C2B9H11)] (X = Cl, Y = K(18-crown-6), L = CO (1), PPh3 (2); X = I, Y = NEt4, L = CO (3)) are reported, and the structureof 3 has been established by an X-ray diffraction study. The anion adopts the "piano stool"structure with the ruthenium atom 5-coordinated on one side by a nido-7,8-C2B9H11 groupand on the other by the CO, PPh3, and I ligands. Treatment of 1 with TlPF6 in THF(tetrahydrofuran) affords solutions of the labile species [Ru(THF)(CO)(PPh3)(5-7,8-C2B9H11)](5), which readily react with a 3-fold excess of the monosubstituted alkynes RC
CH (R =Ph, But, SiMe3). The product from PhCCH is [Ru(CO)(PPh3)(2: 5-9-(E)-C(H)=C(H)Ph-7,8-C2B9H10)] (8), the structure of which was determined by X-ray crystallography. The metalatom is 5-coordinated by the open face of the nido-7,8-C2B9 cage and also 2-coordinated bythe C=C bond of the E-C(H)=C(H)Ph group, the latter being attached to a boron atom in an
-site with respect to the carbons of the CCBB B
: 5-9-C(H)(PMe3)CH2-7,8-C2B9H10)] (15).The NMR data (1H, 13C{1H}, 11B{1H}) are reported and discussed.
5-7,8-C2B9H11)] (X = Cl, Y = K(18-crown-6), L = CO (1), PPh3 (2); X = I, Y = NEt4, L = CO (3)) are reported, and the structureof 3 has been established by an X-ray diffraction study. The anion adopts the "piano stool"structure with the ruthenium atom 5-coordinated on one side by a nido-7,8-C2B9H11 groupand on the other by the CO, PPh3, and I ligands. Treatment of 1 with TlPF6 in THF(tetrahydrofuran) affords solutions of the labile species [Ru(THF)(CO)(PPh3)(5-7,8-C2B9H11)](5), which readily react with a 3-fold excess of the monosubstituted alkynes RCCH (R =Ph, But, SiMe3). The product from PhCCH is [Ru(CO)(PPh3)(2: 5-9-(E)-C(H)=C(H)Ph-7,8-C2B9H10)] (8), the structure of which was determined by X-ray crystallography. The metalatom is 5-coordinated by the open face of the nido-7,8-C2B9 cage and also 2-coordinated bythe C=C bond of the E-C(H)=C(H)Ph group, the latter being attached to a boron atom in an-site with respect to the carbons of the CH gives [Ru(CO)(PPh3)(2: 5-9-(E)-C(H)=C(H)But-10-(E)-C(H)=C(H)But-7,8-C2B9H9)] (9). The 2 bonding mode of the 9-(E)-C(H)=C(H)But group to the metal isdisplaced in reactions with PMe3, CNBut, and CO, yielding the species [Ru(CO)(PPh3)(L)(5-9,10-{(E)-C(H)=C(H)But}2-7,8-C2B9H9)] (L = PMe3 (10), CNBut (11), CO (12)). The alkyneMe3SiCCH reacts with 5 in the presence of traces of moisture to give [Ru(CO)(PPh3)(2: 5-9-C(H)=CH2-7,8-C2B9H10)] (13), having a molecular structure closely related to that of8, as confirmed by an X-ray diffraction study. Compound 13 reacts with CNBut to afford[Ru(CO)(PPh3)(CNBut)(5-9-C(H)=CH2-7,8-C2B9H10)] (14), studied by X-ray diffraction, andwith PMe3 to give the ylide complex [Ru(CO)(PPh3)(: 5-9-C(H)(PMe3)CH2-7,8-C2B9H10)] (15).The NMR data (1H, 13C{1H}, 11B{1H}) are reported and discussed.