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Transition Metal Complexes Coordinated by Water Soluble Phosphane Ligands: How Cyclodextrins Can Alter the Coordination Sphere?

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Transition Metal Complexes Coordinated by Water Soluble Phosphane Ligands: How Cyclodextrins Can Alter the Coordination Sphere? molecules Article Transition Metal Complexes Coordinated by Water Soluble Phosphane Ligands: How Cyclodextrins Can Alter the Coordination Sphere? Michel Ferreira, Hervé Bricout, Sébastien Tilloy and Eric Monflier * University of Artois, CNRS, Centrale Lille, ENSCL, University of Lille, UMR 8181, Unité de Catalyse et de Chimie du Solide (UCCS), F-62300 Lens, France; [email protected] (M.F.); [email protected] (H.B.); [email protected] (S.T.) * Correspondence: eric.monfl[email protected]; Tel.: +33-321-791-772; Fax: +33-321-791-717 Academic Editor: Bernard Martel Received: 9 December 2016; Accepted: 12 January 2017; Published: 17 January 2017 Abstract: The behaviour of platinum(II) and palladium(0) complexes coordinated by various hydrosoluble monodentate phosphane ligands has been investigated by 31P{1H} NMR spectroscopy in the presence of randomly methylated β-cyclodextrin (RAME-β-CD). This molecular receptor can have no impact on the organometallic complexes, induce the formation of phosphane low-coordinated complexes or form coordination second sphere species. These three behaviours are under thermodynamic control and are governed not only by the affinity of RAME-β-CD for the phosphane but also by the phosphane stereoelectronic properties. When observed, the low-coordinated complexes may be formed either via a preliminary decoordination of the phosphane followed by a complexation of the free ligand by the CD or via the generation of organometallic species complexed by CD which then lead to expulsion of ligands to decrease their internal steric hindrance. Keywords: platinum; palladium; TPPTS; cyclodextrin; hydrosoluble organometallic complexes; supramolecular chemistry 1. Introduction Biphasic aqueous organometallic catalysis is one of the greenest solutions to produce organic chemicals [1,2]. Indeed, water is not only cheap and non-toxic, but also permits one to immobilize the catalyst in an aqueous phase by the use of water-soluble ligands, leading to ease of recycling by simple decantation at the end of the reaction [3]. The most widespread ligand used in such systems is TPPTS (tris(3-sulfonatophenyl)phosphane sodium salt, Table1, entry 1) which is responsible for the industrial success of the aqueous biphasic propene hydroformylation (Ruhrchemie-Rhône Poulenc process, 1984) [4]. Attractive for partially water-soluble olefins, this strategy suffers from low catalytic activity when hydrophobic substrates are used due to mass transfer limitations. The alternative approaches to overcome this drawback have been recently reviewed [5,6]. These include the use of cyclodextrins (CDs) which are widely recognized as outstanding water-soluble receptors in aqueous biphasic organometallic processes [7]. These macrocycles were firstly used as phase transfer agents between the organic and the aqueous layers by forming inclusion complexes with a hydrophobic substrate at the interface in order to convert it thanks to a water-soluble organometallic catalyst. However, CDs are more than simple receptors for hydrophobic substrates and can be now considered as polyfunctional entities in aqueous biphasic organometallic catalysis [8]. In particular, CDs can modify the catalytic species involved in the reaction. As an example, when TPPTS is combined with a rhodium precursor to catalyse the 1-decene aqueous biphasic hydroformylation reaction, a linear to branched aldehyde ratio drop is Molecules 2017, 22, 140; doi:10.3390/molecules22010140 www.mdpi.com/journal/molecules Molecules 2017, 22, 140 2 of 25 observedMolecules when 2017, the22, 140 experiment is conducted in the presence of RAME-β-CD (=randomly methylated2 of 25 β-CD) [9]. Under CO/H2 pressure and with RAME-β-CD, equilibria displacements between the CD) [9]. Under CO/H2 pressure and with RAME-β-CD, equilibria displacements between the different different catalytic species towards the formation of phosphane low-coordinated species are observed. catalytic species towards the formation of phosphane low-coordinated species are observed. These These equilibria, displaced by TPPTS inclusion into the CD cavity, are responsible for the drop in equilibria, displaced by TPPTS inclusion into the CD cavity, are responsible for the drop in regioselectivity regioselectivity(Scheme 1) [10]. (Scheme 1)[10]. Molecules 2017, 22, 140 2 of 25 Molecules 2017, 22, 140 2 of 25 Molecules 2017, 22, 140 2 of 25 CD) [9]. Under CO/H2 pressure and with RAME-β-CD, equilibria displacements between the different CD) [9]. Under CO/H2 pressure and with RAME-β-CD, equilibria displacements between the different CD) [9]. Under CO/H2 pressure and with RAME-β-CD, equilibria displacements between the different catalytic species towards the formation of phosphane low-coordinated species are observed. These catalyticScheme species 1. Equilibria towards between the formation the different of phosphane catalytic low-coordinated species during species 1-decene are aqueousobserved. biphasic These Schemeequilibria, 1. Equilibriadisplaced by betweenTPPTS inclusio then different into the CD catalytic cavity, are species responsibl duringe for the 1-decene drop in regioselectivity aqueous biphasic equilibria,hydroformylation displaced byassisted TPPTS by inclusio RAME-n intoβ-CD. the CD cavity, are responsible for the drop in regioselectivity hydroformylation(Scheme 1) [10]. assisted by RAME-β-CD. (Scheme 1) [10]. Along the same lines, when a water-soluble triphenylphosphane derivative possessing a higher Alongaffinity thetowards same CDs lines, is wheninvolved a water-solublein a rhodium HRhCOL triphenylphosphane3 type species derivative(L = p-tBuPhP( possessingm-PhSO3Na) a higher2 affinityphosphane), towards CDsunsaturated is involved catalytic in aspecies rhodium are HRhCOLalso formed3 type in the species presence (L =ofp -tBuPhP(CD even mwhen-PhSO the3 Na)2 phosphane),organometallic unsaturated complex was catalytic not exposed species to a are CO/H also2 atmosphere formed in [11]. the presence of CD even when the organometallicTable 1. complex Structure,was abbreviation not exposed of the water-soluble to a CO/H 2phosphanesatmosphere used, [11 and]. value of the association Thisconstant behaviour, (K) for the not inclusion observed complexes with between TPPTS, the wasRAME- attributedβ-CD and the to phosphane. the more stable inclusion complexEntry formed betweenStructure the CD and the phosphane,Name due Abbreviation to the presence of the well-recognizedK (M−1) a,b p-tert-butylphenyl group. Moreover, it has been demonstrated that the combination of the same tris(3-sodium-sulfonatophenyl)phosphane 1 840 [15] ligand with another metal centre, e.g., palladium or platinum,TPPTS led to the same behaviour, that is to say formation of low-coordinated organometallic species [12]. However,Scheme the 1. combination EquilibriaEquilibria betweenbetween of a thethe palladium differentdifferenttris(4-methyl-3-sodium-sul catalyticcatalytic precursor speciesspecies with duringduring afonatophenyl)phosphane water-soluble1-decene1-decene aqueousaqueous triphenylphosphanebiphasicbiphasic 2 Scheme 1. Equilibria between the different catalytic species during 1-decene aqueous biphasic 960 [15] hydroformylation assisted by RAME-β-CD. tris(p-Me)TPPTS derivative possessinghydroformylation a p assisted-tert-butylbiphenyl by RAME-β-CD. group led to the formation of a stable second-sphere coordination adduct where the CD encapsulated the ligand directly bounded to the metal centre [13]. Along the same lines, when a water-solubletris(4-methoxy-3-sodium-sulfonatophenyl)phosphane triphenylphosphane derivative possessing a higher 3 Along the same lines, when a water-soluble triphenylphosphane derivative possessing a higher0 [15] Such speciesaffinity had towards already CDs beenis involved observed in a rhodium with a phosphaneHRhCOL3 tris(type bearingp -OMe)TPPTSspecies adamantyl(L = p-tBuPhP( groupsm-PhSO [3Na)14].2 affinity towards CDs is involved in a rhodium HRhCOL3 type species (L = p-tBuPhP(m-PhSO3Na)2 affinity towards CDs is involved in a rhodium HRhCOL3 type species (L = p-tBuPhP(m-PhSO3Na)2 phosphane), unsaturated catalytic species are also formed in the presence of CD even when the phosphane), unsaturated catalytic species are also formed in the presence of CD even when the organometallic complex was not exposed to a CO/H2 atmosphere [11]. Tableorganometallic 1. Structure, complex abbreviation was not exposed of the water-soluble to atris(6-methyl-3-sodium-sul CO/H2 atmosphere phosphanes [11]. fonatophenyl)phosphane used, and value of the association organometallic4 complex was not exposed to a CO/H2 atmosphere [11]. 0 [15] constantTable (K) for1. Structure,Structure, the inclusion abbreviationabbreviation complexes ofof thethe water-solublewater-soluble between the phosphanes RAME-tris(βo used,-CD-Me)TPPTS andand value the phosphane. of the association Table 1. Structure, abbreviation of the water-soluble phosphanes used, and value of the association constantTable 1. Structure,(K) for the abbreviationinclusion complexes of the water-soluble between the RAME-phosphanesβ-CD used, and the and phosphane. value of the association constant (K) for the inclusion complexes between the RAME-β-CD and the phosphane. constant (K) for the inclusion complexes between the RAME-β-CD and the phosphane. −1 a,b Entry Structuretris(6-methoxy-3-sodium-sulfonatophenyl)phosphane Name Abbreviation K−1 (Ma,b ) Entry Structure Name Abbreviation K (M−1) a,b 5 Entry Structure Name Abbreviation K (M−1) a,b0 [15] Entry Structure Nametris(
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