η5 η3 Hapticity Interconversion in Cycloheptadienyl Molybdenum Complexes

DOI: 10.1039/DT9940002303

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2303 - 2312 (1994)

Update date:2022-08-04

Topics:

Authors:

Beddoes, Roy L.

Hinchliffe, Jonathan R.

Souza, Ana-Lucia A. B. de

Whiteley, Mark W.

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1039/DT9940002303

A series of reactions of the general type 2(η⁵-C7H9)>(1+) + L' -> 2(η³-C7H9)>(1+), involving η⁵ -> η³ hapticity conversion at a molybdenum co-ordinated cycloheptadienyl ring, have been examined.The specific examples investigated comprise reactions of 5-C7H9)>(1+) 2 = 2,2'-bipyridyl (bipy) 1, Ph2PCH2PPh2 (dppm) 6, Ph2PCH2CH2PPh2 (dppe) 7; L = CNtBu 17 or PPh3 18> with NCMe or CNtBu.Complex 1 reacts reversibly with NCMe to give 3-C7H9)>(1+) 2 and, in NCMe, 7 exists as an equilibrium mixture with 3-C7H9)>(1+) 8.The complexes 6, 17 and 18 do not react with NCMe at ambient temperature.Treatment of 1, 6 and 7 with CNtBu affords 2(η³-C7H9)>(1+) (L₂ = bipy 4, dppm 9 or dppe 11) although 4 is better prepared by reaction of 3-C7H9)>(1+) 5 with bipy.Complex 4 is resistant to carbonyl elimination but 9 and 11 undergo facile loss of CO to give 2(η⁵-C7H9)>(1+) (L₂ = dppm 10 or dppe 12 so establishing examples of associative ligand-substitution processes which proceed with η⁵ -> η³ -> η⁵ hapticity interconversion at the C7H9 dienyl ligand.The reaction between 17 and CNtBu affords 5-C7H9)>(1+) 19 with no observable η³-C7H9 intermediate but 19 reacts with further CNtBu to yield 3-C7H9)>(1+) 20.The crystal structures of complexes 1 and 4 have been determined.Complex 1 adopts an asymmetric ligand arrangement similar to that previously described for 6.Complex 4 has a pseudo-octahedral molecular geometry in which CNtBu is located trans to the η³-bonded C7H9 ligand.

Full text of DOI:10.1039/DT9940002303

View Article Online / Journal Homepage / Table of Contents for this issue

View Article Online

Products guided by the article

Product name:[Mo(CO)(CNt-Bu)2(dppe)(η3-C7H9)]BF4

Cas No:159026-75-2

R&D Labs maybe for 159026-75-2

Hawks Chemical

Contact:+44 (0)161 367 9441

Address:
H&Y International Group Ltd

Contact:+86-571-86491666

Address:SHI XIANG ROAD
LinHai Cina Chemical Co., LTD.

Contact:0576-85580989

Address:Pharma-chem zone,Duqiao,Linhai,Zhejiang,China
Sichuan Sangao Biochemical Co., Ltd

Contact:+86-28-84874233

Address:19F, Bldg.2, Shudu Center, Tianfu 2nd St., Hi-tech zone, Chengdu 610041, Sichuan Province, China.
SHANGHAI GILEADER ADVANCE MATERIAL TECHNOLOGY CO.,LTD

website:http://www.tanguitech.com/contact.asp

Contact:+86-021-58692556

Address:No.6 Building,No. 668 Hengan RD Pudong,Shanghai

Relevant to this article

PHARMACOLOGICAL PROPERTIES OF THE PRODUCTS OF THE REACTION OF EPITHIOCHLOROHYDRIN WITH BENZIMIDAZOLES

Doi:10.1007/BF00772996
(1993)
Rational design of a redox-labeled chiral target for an enantioselective aptamer-based electrochemical binding assay

Doi:10.1002/chem.201302979
(2014)
Asymmetric michael addition of oxindoles to allenoate catalyzed by N-acyl aminophosphine: Construction of functionalized oxindoles with quaternary stereogenic center

Doi:10.1002/adsc.201300695
(2014)
Synthetic and mechanistic studies on the azabicyclo[7.3.1]enediyne core and naphtho[2,3-h]quinoline portions of dynemicin A

Doi:10.1021/ja970435v
(1997)
The identification, analysis and structure-based development of novel inhibitors of 6-hydroxymethyl-7,8-dihydropterin pyrophosphokinase

Doi:10.1016/j.bmc.2014.02.022
(2014)
Asymmetric semipinacol rearrangement of 2,3-allenols with N-bromo-1,8-naphthalimide

Doi:10.1039/c4cc00767k
(2014)

Article Doi