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Reaction of an N/Al FLP-Based Aluminum Hydride toward Alkyne: Deprotonated Alumination versus Hydroalumination with Regioselective cis-Addition Character

Abstract

Reactions of an N/Al FLP-based aluminum dihydride (o-TMP-C6H4)AlH2 (1, TMP = N(CMe2CH2)2CH2) with several terminal and internal alkynes are studied. 1 reacted with HC≡CR by deprotonated alumination to yield (o-TMP-C6H4)Al(C≡CR)2 (R = Ph (2), 1-C4H3S (3)) and with HC≡CPPh2 by deprotonated alumination followed with the HC≡CPPh2 C(sp)‒H-activation addition to [o-(TMP)H-C6H4]Al(C≡CPPh2)3 (4), respectively. Furthermore, 1 reacted with R1C≡CR2 to produce mono-hydroalumination compounds (o-TMP-C6H4)AlH(CR1=CHR2) (R1,R2 = Ph,Ph (5), Ph,Et (6), SiHMeR',Ph (7, R' = N(SiMe2Ph)-2,6-iPr2C6H3), all as a monomer, as well as {(o-TMP-C6H4)AlH[C(PPh2)=CHPh]}2 (8) being a dimer formed due by the intermolecular P/Al donor-acceptor interaction. Also produced were the bis-hydroalumination compounds (o-TMP-C6H4)Al(CR1=CHR2)2 (R1,R2 = SiHMe2,PPh2 (9), SiHPh2,PPh2 (10)). The NBO analysis was performed, which revealed the inequivalent charge distribution on the C≡C carbon atoms of the alkynes that have two different substituents. The electronic matching interaction between the Al‒H and C≡C bonds was discussed. The hydroalumination reaction exhibits the regioselective cis-addition character.

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Publication details

The article was received on 28 Feb 2019, accepted on 15 May 2019 and first published on 17 May 2019


Article type: Paper
DOI: 10.1039/C9DT00903E
Dalton Trans., 2019, Accepted Manuscript

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    Reaction of an N/Al FLP-Based Aluminum Hydride toward Alkyne: Deprotonated Alumination versus Hydroalumination with Regioselective cis-Addition Character

    H. Zhu, Y. Chen, W. Jiang, B. Li, G. Fu and S. Chen, Dalton Trans., 2019, Accepted Manuscript , DOI: 10.1039/C9DT00903E

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