酸催化Mo(NAr)(CR1R2)(OR)2配合物及其Mo(NAr)(烯烃)(OR)2异构体(Ar = 2,6-i- pr2c6h3, OR = OSiPh3或OAr)相互转化的探索

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2023-08-04 DOI:10.1021/acs.organomet.3c00237

Sumeng Liu, Richard R. Schrock*, Matthew P. Conley, Charlene Tsay and Veronica Carta,

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Addition of [(Et2O)2H][B(C6F5)4] to the alkylidene complexes generates cationic 12e alkyl complexes [Mo(NAr)(CHMe2)(OSiPh3)2]+, [Mo(NAr)(CHMeCH2Ph)(OSiPh3)2]+, [Mo(NAr)(CHEtPh)(OSiPh3)2]+, and [Mo(NAr)(CH2CH2Ph)(OSiPh3)2]+. Deprotonation of the cationic alkyl complexes by NEt3 generates the disubstituted alkylidene complexes as the major product. In the case of [Mo(NAr)(CHMeCH2Ph)(OSiPh3)2]+, both Mo(NAr)(CMeCH2Ph)(OSiPh3)2 and Mo(NAr)(CH2═CHCH2Ph)(OSiPh3)2 are formed initially ([alkylidene]/[olefin] = 1.5:1), but the latter then isomerizes to Mo(NAr)(CH3CH═CHPh)(OSiPh3)2. [Mo(NAr)(CHMePh)(OAr)2][B(C6F5)4] was prepared through the protonation of Mo(NAr)(CMePh)(OAr)2 with [(Et2O)2H][B(C6F5)4]. Mo(NAr)(CMePh)(OAr)2 does not react with [PhNMe2H][B(C6F5)4] at room temperature. 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引用次数: 1

摘要

四种新的Mo(NAr)(CR1R2)(OSiPh3)2配合物(Ar = 2,6-i- pr2c6h3;CR1R2 = CMe2, CMeCH2Ph, CEtPh，或CHCH2Ph)是通过CH2 CR1R2加入到新戊二烯或新茶碱络合物中制备的。以Mo(NAr)(CH2 = CH2)(OSiPh3)2为原料制备了三种化学式为Mo(NAr)(烯烃)(OSiPh3)2的新型烯烃配合物，即Mo(NAr)(trans-CH3CH = CHPh)(OSiPh3)2、Mo(NAr)(CH2 = CMePh)(OSiPh3)2和Mo(NAr)(CH2 = CHCMe3)(OSiPh3)2。其它烯烃配合物的合成由于烯烃的顺/反异构化和烯烃碳链内C = C键的异构化而变得复杂。在烷基烯配合物中加入[(Et2O)2H][B(C6F5)4]生成阳离子12e烷基配合物[Mo(NAr)(CHMe2)(OSiPh3)2]+、[Mo(NAr)(CHMeCH2Ph)(OSiPh3)2]+、[Mo(NAr)(CHMeCH2Ph)(OSiPh3)2]+和[Mo(NAr)(CH2CH2Ph)(OSiPh3)2]+。阳离子烷基配合物经NEt3脱质子反应生成二取代烷基配合物为主要产物。在[Mo(NAr)(CHMeCH2Ph)(OSiPh3)2]+的情况下，Mo(NAr)(CMeCH2Ph)(OSiPh3)2和Mo(NAr)(CH2 = CHCH2Ph)(OSiPh3)2最初形成([烷基烯]/[烯烃]= 1.5:1)，但后者随后异构化为Mo(NAr)(CH3CH CHPh)(OSiPh3)2。由Mo(NAr)(CMePh)(OAr)2与[(Et2O)2H][B(C6F5)4]质子化反应制得[Mo(NAr)(CHMePh)(OAr)2][B(C6F5)4]。Mo(NAr)(CMePh)(OAr)2在室温下不与[PhNMe2H][B(C6F5)4]发生反应。Mo(NAr)(CH2 CH2)(OAr)2在室温下在溶液中分解生成Mo(NAr)(OAr)(η1，η2-2-异丙基-6-(pro- 1-en-2-基)苯酚)(Et2O)，通过在OAr配体的异丙基中活化，然后损失乙烷;Mo(NAr)(CH2 CHPh)(OAr)2的分解类似。本文报道了8项单晶x射线衍射研究。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

An Exploration of the Acid-Catalyzed Interconversion of Mo(NAr)(CR1R2)(OR)2 Complexes and Their Mo(NAr)(Olefin)(OR)2 Isomers (Ar = 2,6-i-Pr2C6H3, OR = OSiPh3 or OAr)

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An Exploration of the Acid-Catalyzed Interconversion of Mo(NAr)(CR1R2)(OR)2 Complexes and Their Mo(NAr)(Olefin)(OR)2 Isomers (Ar = 2,6-i-Pr2C6H3, OR = OSiPh3 or OAr)

Four new Mo(NAr)(CR1R2)(OSiPh₃)₂ complexes (Ar = 2,6-i-Pr₂C₆H₃; CR1R2 = CMe₂, CMeCH₂Ph, CEtPh, or CHCH₂Ph) were prepared through addition of CH₂═CR1R2 to a neopentylidene or a neophylidene complex. Three new olefin complexes with the formula Mo(NAr)(olefin)(OSiPh₃)₂ were prepared from Mo(NAr)(CH₂═CH₂)(OSiPh₃)₂, namely, Mo(NAr)(trans-CH₃CH═CHPh)(OSiPh₃)₂, Mo(NAr)(CH₂═CMePh)(OSiPh₃)₂, and Mo(NAr)(CH₂═CHCMe₃)(OSiPh₃)₂. Syntheses of other olefin complexes were complicated by relatively facile cis/trans isomerization of the olefin and isomerization of the C═C bond within the olefin carbon chain. Addition of [(Et₂O)₂H][B(C₆F₅)₄] to the alkylidene complexes generates cationic 12e alkyl complexes [Mo(NAr)(CHMe₂)(OSiPh₃)₂]⁺, [Mo(NAr)(CHMeCH₂Ph)(OSiPh₃)₂]⁺, [Mo(NAr)(CHEtPh)(OSiPh₃)₂]⁺, and [Mo(NAr)(CH₂CH₂Ph)(OSiPh₃)₂]⁺. Deprotonation of the cationic alkyl complexes by NEt₃ generates the disubstituted alkylidene complexes as the major product. In the case of [Mo(NAr)(CHMeCH₂Ph)(OSiPh₃)₂]⁺, both Mo(NAr)(CMeCH₂Ph)(OSiPh₃)₂ and Mo(NAr)(CH₂═CHCH₂Ph)(OSiPh₃)₂ are formed initially ([alkylidene]/[olefin] = 1.5:1), but the latter then isomerizes to Mo(NAr)(CH₃CH═CHPh)(OSiPh₃)₂. [Mo(NAr)(CHMePh)(OAr)₂][B(C₆F₅)₄] was prepared through the protonation of Mo(NAr)(CMePh)(OAr)₂ with [(Et₂O)₂H][B(C₆F₅)₄]. Mo(NAr)(CMePh)(OAr)₂ does not react with [PhNMe₂H][B(C₆F₅)₄] at room temperature. Mo(NAr)(CH₂═CH₂)(OAr)₂ decomposes in solution at room temperature to yield Mo(NAr)(OAr)(η¹,η²-2-isopropyl-6-(prop-1-en-2-yl)phenolate)(Et₂O) through CH activation in the isopropyl group of the OAr ligand followed by loss of ethane; Mo(NAr)(CH₂═CHPh)(OAr)₂ decomposes similarly. Eight single-crystal X-ray diffraction studies are reported.

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.