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Reactivity of a Borane-Appended 1,1′-Bisphosphinoferrocene Ligand: Transition Metal and Lewis Acid Coordination, Cyclopentadienyl Ring Borylation, and Boronium Cation Generation
Organometallics ( IF 2.5 ) Pub Date : 2018-03-06 00:00:00 , DOI: 10.1021/acs.organomet.8b00021
Bradley E. Cowie 1 , David J. H. Emslie 1
Affiliation  

The reaction of a borane-appended analogue of 1,1′-bis(phosphino)ferrocene, [Fe(η5-C5H4PPh2)(η5-C5H4PtBu{(o-BPh2)C6H4})] (FcPPB), with [W(CO)6] under photochemical conditions lead to [W(CO)4(FcPPB*)] (1) (FcPPB* = [Fe(η5-C5H4PPh2){η5-C5H3P(tBu)C6H4-o-BPh}]), in which the borane has added to a cyclopentadienyl ring of the ligand backbone and benzene has been eliminated. Formation of 1 did not occur under thermal conditions, and benzene solutions of the free FcPPB ligand were unreactive under both photochemical and refluxing conditions. Boranes of greater Lewis acidity than the pendent triarylborane of FcPPB were introduced to free FcPPB in an effort to promote intramolecular electrophilic borylation of the ferrocene backbone by eliminating the borane–phosphine interaction in FcPPB. However, addition of B(C6F5)3 provided [Fe(η5-C5H4PPh2{B(C6F5)3})(η5-C5H4PtBu{C6H4(BPh2)-o})], FcPPB{B(C6F5)3} (2), in which B(C6F5)3 forms an adduct with the −PPh2 group, and the intramolecular phosphine–borane interaction present in free FcPPB is maintained in 2. Furthermore, addition of two equiv of BF3(OEt2) to FcPPB yielded a single diastereomer of [Fe(η5-C5H4PPh2)(η5-C5H4PtBu{C6H4(BPh)-o})][BF4] (3), in which one B-phenyl substituent has been abstracted to generate a boronium cation {BR2L2+}. Reaction of FcPPB with [AuCl(PPh3)]/GaCl3 afforded dimetallic [{Au(FcPPB)}2][GaCl4]2 (4) as a mixture of diastereomers featuring μ-1κP:2κP′-coordination of each FcPPB ligand and a near linear geometry at each gold(I) center. The pendent borane in 4 interacts only weakly or not at all with gold, but electrophilic addition of the borane to the ferrocene backbone was not observed upon UV irradiation.

中文翻译:

硼烷附加的1,1'-双膦二茂铁配体的反应活性:过渡金属和路易斯酸配位,环戊二烯基环硼化和硼阳离子生成

的1,1'-双硼烷-所附类似物的反应(膦基)二茂铁,的[Fe(η 5 -C 5 H ^ 4 PPH 2)(η 5 -C 5 H ^ 4 P卜{(Ô -BPh 2)C 6 H ^ 4 })](FcPPB)中,用[W(CO)6 ]下光化学条件导致[W(CO)4(FcPPB *)](1)(FcPPB * = [铁(η 5 -C 5 ħ 4 PPH 2){η 5 -C 5 H ^ 3 P(卜)C6 ħ 4 - ö -BPh}]),其中,所述硼烷已加入到该配体骨架和苯的环戊二烯基环已被淘汰。在热条件下不会发生1的形成,游离FcPPB配体的苯溶液在光化学和回流条件下均不反应。将路易斯酸度比FcPPB侧基三芳基硼烷高的硼烷引入到游离FcPPB中,以通过消除FcPPB中的硼烷-膦相互作用来促进二茂铁主链的分子内亲电硼化。然而,添加B(C 6 ˚F 53提供的[Fe(η 5 -C 5 H ^ 4 PPH2 {B(C 6 ˚F 53 })(η 5 -C 5 H ^ 4 P卜{C 6 H ^ 4(BPH 2) - ö })],FcPPB {B(C 6 ˚F 53 }(2),其中B(C 6 F 53-P Ph 2基团形成加合物,游离FcPPB中存在的分子内膦-硼烷相互作用保持在2中。此外,添加了两个当量的BF 3(OEt2)以产生FcPPB的单一非对映的[Fe(η 5 -C 5 H ^ 4 PPH 2)(η 5 -C 5 H ^ 4 P卜{C 6 H ^ 4(BPH) - ö })] [BF 4 ] (3),其中一个B-苯基取代基已被提取以产生硼阳离子{BR 2 L 2 + }。FcPPB与[AuCl(PPh 3)] / GaCl 3反应得到双金属[{Au(FcPPB)} 2 ] [GaCl 4 ] 24)非对映体配μ-1κ的混合物P:2κ P配体在每个金(I)中心的每个FcPPB的'-coordination和接近线性的几何形状。4中的悬垂硼烷仅与金微弱地相互作用或根本不相互作用,但是在紫外线照射下未观察到硼烷向二茂铁主链的亲电加成。
更新日期:2018-03-07
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