钌的夹心型双氧络合物的制备及反应性。

Preparation and reactivity of half-sandwich dioxygen complexes of ruthenium.

机构信息

Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia, Via Torino 155, 30172 Venezia Mestre, Italy.

出版信息

Dalton Trans. 2018 Jul 10;47(27):9173-9184. doi: 10.1039/c8dt01871e.

DOI:10.1039/c8dt01871e

PMID:29946597

Abstract

Dioxygen complexes [Ru(η5-C5Me5)(η2-O2){P(OEt)3}2]BPh4 (1) and [Ru(η5-C5Me5)(η2-O2)(PPh3){P(OR)3}]BPh4 (2, 3) [R = Me (2), Et (3)] were prepared by allowing chloro-complexes RuCl(η5-C5Me5)[P(OEt)3]2 and RuCl(η5-C5Me5)(PPh3)[P(OR)3] to react with air (1 atm) in the presence of NaBPh4. Substitution of the η2-O2 in 1-3 by alkenes [CH2[double bond, length as m-dash]CH2, [upper bond 1 start]CH[double bond, length as m-dash]CHCO(O)C[upper bond 1 end]O] and terminal alkynes (PhC[triple bond, length as m-dash]CH) afforded [Ru(η5-C5Me5)(η2-CH2[double bond, length as m-dash]CH2){P(OEt)3}L]BPh4 (4) [L = P(OEt)3 (a), PPh3 (b)], [Ru(η5-C5Me5){η2-[upper bond 1 start]CH[double bond, length as m-dash]CHCO(O)C[upper bond 1 end]O}{P(OEt)3}2]BPh4 (5) and [Ru(η5-C5Me5){[double bond, length as m-dash]C[double bond, length as m-dash]C(H)Ph}{P(OEt)3}2]BPh4 (6) derivatives. Protonation of dioxygen complexes 1-3 with triflic acid yielded phosphate complexes [Ru(κ1-OTf)(η5-C5Me5){P(O)(OEt)3}2] (7) and [Ru(κ1-OTf)(η5-C5Me5){P(O)Ph3}{P(O)(OMe)3}] (8). A reaction path for the formation of complexes 7 and 8 is proposed by DFT studies. Besides phosphate complex 7, protonation of 1 under a CH2[double bond, length as m-dash]CH2 atmosphere (1 atm) afforded acetic acid. Treatment of complexes 7 and 8 with tBuNC afforded the tris(isocyanide) derivative [Ru(η5-C5Me5)(tBuNC)3]BPh4 (9). The complexes were characterised spectroscopically (IR and NMR) and by X-ray crystal structure determination of 1, 2 and 3.

摘要

二氧配合物[Ru(η5-C5Me5)(η2-O2){P(OEt)3}2]BPh4(1)和[Ru(η5-C5Me5)(η2-O2)(PPh3){P(OR)3}]BPh4(2,3)[R=Me(2), Et(3)]是通过让氯配合物RuCl(η5-C5Me5)[P(OEt)3]2和RuCl(η5-C5Me5)(PPh3)[P(OR)3]与空气中的氧气(1atm)在NaBPh4的存在下反应而制备的。在 1-3 中，通过烯烃[CH2[double bond, length as m-dash]CH2，[upper bond 1 start]CH[double bond, length as m-dash]CHCO(O)C[upper bond 1 end]O]和末端炔烃(PhC[triple bond, length as m-dash]CH)取代η2-O2，得到[Ru(η5-C5Me5)(η2-CH2[double bond, length as m-dash]CH2){P(OEt)3}L]BPh4(4)[L=P(OEt)3(a)，PPh3(b)]，[Ru(η5-C5Me5){η2-[upper bond 1 start]CH[double bond, length as m-dash]CHCO(O)C[upper bond 1 end]O}{P(OEt)3}2]BPh4(5)和[Ru(η5-C5Me5){[double bond, length as m-dash]C[double bond, length as m-dash]C(H)Ph}{P(OEt)3}2]BPh4(6)衍生物。用三氟磺酸与二氧配合物 1-3 进行质子化反应，得到磷酸酯配合物Ru(κ1-OTf)(η5-C5Me5){P(O)(OEt)3}2和[Ru(κ1-OTf)(η5-C5Me5){P(O)Ph3}{P(O)(OMe)3}]BPh4(8)。通过密度泛函理论研究提出了形成配合物 7 和 8 的反应途径。除了磷酸酯配合物 7 之外，在 CH2[double bond, length as m-dash]CH2气氛(1atm)下对 1 进行质子化反应还得到了乙酸。用 tBuNC 处理配合物 7 和 8，得到三异氰化物衍生物[Ru(η5-C5Me5)(tBuNC)3]BPh4(9)。通过光谱学(IR 和 NMR)和 1、2 和 3 的 X 射线晶体结构测定对配合物进行了表征。