Differential Reactivity of [TpRu(κ
<sup>2</sup>
<i>P</i>
,
<i>N</i>
‐
<i>i</i>
Pr
<sub>2</sub>
PXPy)Cl] (X = NH, S) Bearing Hemilabile Coligands Towards NaBAr
<sup>F</sup>
<sub>4</sub>
, Lithium Acetylide, and Acetylenes
作者:Vinay K. Singh、M. Carmen Puerta、Pedro Valerga
DOI:10.1002/ejic.201500082
日期:2015.4
N-iPr2PSPy)][BArF4] have been efficiently synthesized from 1a and 1b. The methoxy(methyl)carbene complexes [TpRu=C(OMe)CH3}(κ2P,N-iPr2PXPy)][BPh4] [X = NH (5a), S (5b)] were isolated from the reactions of 1a and 1b with acetylene gas in the presence of NaBArF4 in methanol. The deprotonation of the cationic vinylidenes derived from 1b with KtBuO affords the corresponding neutral acetylide complexes, which undergo facile
与 [TpRu(κ2P,N-iPr2PNHPy)Cl] (1a, Tp = trispyrazolylborate) 相比,[TpRu(κ2P,N-iPr2PSPy)Cl] (1b) 与四[3,5-双(三氟甲基)苯基钠反应]硼酸盐 (NaBArF4) 在氮气氛下的氟苯中得到双核复合物 [TpRu(κ2P,N-iPr2PSPy)}2(μ-Cl)][BArF4] (1b')。通过多种合成策略,一系列中性乙炔化合物 [TpRu(C≡CR)(κ2P,N-iPr2PXHPy)] [X = NH; R = Ph (2a)、SiMe3 (2b);X = S; R = Ph (2c), p-C6H4Br (2d), COOMe (2e)],阳离子亚乙烯基络合物 [TpRu(=C=CHR)(κ2P,N-iPr2PNHPy)]+ [X = NH; R = Ph (3a)、SiMe3 (3b);X = S; R