Diastereoselective synthesis and coordination chemistry of enantiopure keto-bis-(2-phosphametallocene)s

Duncan Carmichael; Xavier F. Le Goff; Eric Muller; Louis Ricard; Marek Stankevi

doi:10.1039/c2dt11647b

Diastereoselective synthesis and coordination chemistry of enantiopure keto-bis-(2-phosphametallocene)s

Duncan Carmichael
, Xavier F. Le Goff
, Eric Muller
, Louis Ricard
, Marek Stankevi

CNRS
University of Maria Curie-Skodowska

Research output: Contribution to journal › Article › peer-review

Abstract

Enantiopure 2-(chlorocarbonyl)phosphametallocenes [MCp*(2-{COCl}-3,4- Me ₂-5-Ph-PC ₄)] (M = Fe, Ru) react with phospholide anions to give 2-phosphametallocene-2′-acylphospholides K[MCp*(2-CO- 2′-{3′,4′-Me ₂-5′-PhPC ₄}-3,4- Me ₂-5-Ph-PC ₄)] (M = Fe, Ru) and these have been converted into keto-bis-(2-phosphametallocene)s through reaction with [FeClCp* (tmeda)]; templation of this process with CuBr gives rise to the C ₂- (or pseudo-C ₂- when M = Ru) symmetric form of [{MCp*(3,4- Me ₂-5-Ph-PC ₄)} ₂-2,2′-(CO)] (M = Fe, Ru; Fe, Fe) with high (>95%) diastereoselectivity. X-Ray structures of these ligands coordinated to [RuCp*Cl] and [PtCl ₂] centres show that the spatial orientation of the very flexible keto-bis-(2-phosphametallocene) structure is highly responsive to the coordination sphere of the chelated platinum or ruthenium centre.

Original language	English
Pages (from-to)	5155-5162
Number of pages	8
Journal	Dalton Transactions
Volume	41
Issue number	17
DOIs	https://doi.org/10.1039/c2dt11647b
Publication status	Published - 7 May 2012
Externally published	Yes

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@article{f672397b15dd426eba63077fba4ceb70,

title = "Diastereoselective synthesis and coordination chemistry of enantiopure keto-bis-(2-phosphametallocene)s",

abstract = "Enantiopure 2-(chlorocarbonyl)phosphametallocenes [MCp*(2-\{COCl\}-3,4- Me 2-5-Ph-PC 4)] (M = Fe, Ru) react with phospholide anions to give 2-phosphametallocene-2′-acylphospholides K[MCp*(2-CO- 2′-\{3′,4′-Me 2-5′-PhPC 4\}-3,4- Me 2-5-Ph-PC 4)] (M = Fe, Ru) and these have been converted into keto-bis-(2-phosphametallocene)s through reaction with [FeClCp* (tmeda)]; templation of this process with CuBr gives rise to the C 2- (or pseudo-C 2- when M = Ru) symmetric form of [\{MCp*(3,4- Me 2-5-Ph-PC 4)\} 2-2,2′-(CO)] (M = Fe, Ru; Fe, Fe) with high (>95\%) diastereoselectivity. X-Ray structures of these ligands coordinated to [RuCp*Cl] and [PtCl 2] centres show that the spatial orientation of the very flexible keto-bis-(2-phosphametallocene) structure is highly responsive to the coordination sphere of the chelated platinum or ruthenium centre.",

author = "Duncan Carmichael and \{Le Goff\}, \{Xavier F.\} and Eric Muller and Louis Ricard and Marek Stankevi",

year = "2012",

month = may,

day = "7",

doi = "10.1039/c2dt11647b",

language = "English",

volume = "41",

pages = "5155--5162",

journal = "Dalton Transactions",

issn = "1477-9226",

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TY - JOUR

T1 - Diastereoselective synthesis and coordination chemistry of enantiopure keto-bis-(2-phosphametallocene)s

AU - Carmichael, Duncan

AU - Le Goff, Xavier F.

AU - Muller, Eric

AU - Ricard, Louis

AU - Stankevi, Marek

PY - 2012/5/7

Y1 - 2012/5/7

N2 - Enantiopure 2-(chlorocarbonyl)phosphametallocenes [MCp*(2-{COCl}-3,4- Me 2-5-Ph-PC 4)] (M = Fe, Ru) react with phospholide anions to give 2-phosphametallocene-2′-acylphospholides K[MCp*(2-CO- 2′-{3′,4′-Me 2-5′-PhPC 4}-3,4- Me 2-5-Ph-PC 4)] (M = Fe, Ru) and these have been converted into keto-bis-(2-phosphametallocene)s through reaction with [FeClCp* (tmeda)]; templation of this process with CuBr gives rise to the C 2- (or pseudo-C 2- when M = Ru) symmetric form of [{MCp*(3,4- Me 2-5-Ph-PC 4)} 2-2,2′-(CO)] (M = Fe, Ru; Fe, Fe) with high (>95%) diastereoselectivity. X-Ray structures of these ligands coordinated to [RuCp*Cl] and [PtCl 2] centres show that the spatial orientation of the very flexible keto-bis-(2-phosphametallocene) structure is highly responsive to the coordination sphere of the chelated platinum or ruthenium centre.

AB - Enantiopure 2-(chlorocarbonyl)phosphametallocenes [MCp*(2-{COCl}-3,4- Me 2-5-Ph-PC 4)] (M = Fe, Ru) react with phospholide anions to give 2-phosphametallocene-2′-acylphospholides K[MCp*(2-CO- 2′-{3′,4′-Me 2-5′-PhPC 4}-3,4- Me 2-5-Ph-PC 4)] (M = Fe, Ru) and these have been converted into keto-bis-(2-phosphametallocene)s through reaction with [FeClCp* (tmeda)]; templation of this process with CuBr gives rise to the C 2- (or pseudo-C 2- when M = Ru) symmetric form of [{MCp*(3,4- Me 2-5-Ph-PC 4)} 2-2,2′-(CO)] (M = Fe, Ru; Fe, Fe) with high (>95%) diastereoselectivity. X-Ray structures of these ligands coordinated to [RuCp*Cl] and [PtCl 2] centres show that the spatial orientation of the very flexible keto-bis-(2-phosphametallocene) structure is highly responsive to the coordination sphere of the chelated platinum or ruthenium centre.

UR - https://www.scopus.com/pages/publications/84859791406

U2 - 10.1039/c2dt11647b

DO - 10.1039/c2dt11647b

M3 - Article

AN - SCOPUS:84859791406

SN - 1477-9226

VL - 41

SP - 5155

EP - 5162

JO - Dalton Transactions

JF - Dalton Transactions

IS - 17

ER -

Diastereoselective synthesis and coordination chemistry of enantiopure keto-bis-(2-phosphametallocene)s

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