Ligand C–C bond cleavage on ruthenium: observation of a reversible ruthenium(V)–imido/ruthenium(II)–amine couple and X-ray crystal structure of [Ru(bpy)2(NHCMe2)2](PF6)2(bpy = 2,2′-bipyridine)

1992 ◽  
pp. 754-756 ◽  
Author(s):  
Kwok-Yin Wong ◽  
Chi-Ming Che ◽  
Chi-Keung Li ◽  
Wing-Hong Chiu ◽  
Zhong-Yuan Zhou ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Bond Cleavage ◽  
X Ray

scholarly journals Hybrid P,E Ligands: Synthesis, Coordination Chemistry and Catalysis

2021 ◽  
Author(s):  
◽  
Kathryn Mary Allan
Keyword(s):  
Crystal Structure ◽  
Bond Cleavage ◽  
Cone Angle ◽  
Initial Step ◽  
Catalyst Loading ◽  
Bidentate Coordination ◽  
X Ray ◽  
Coordination Modes ◽  
Bite Angle ◽  
Carbon Carbon Bond

<p>This thesis provides an account of research into a family of novel hybrid P,E ligands containing an o-xylene backbone. A methodology for the synthesis of these ligands has been developed, and their coordination behaviour with platinum(II) and platinum(0) precursors has been explored, with particular focus on a phosphinethioether (P,S) ligand of this type. The coordination modes of this P,S ligand with palladium precursors have also been investigated, and the utility of the ligand in a palladium and copper co-catalysed Sonogashira carbon-carbon bond-forming reaction has been evaluated. A range of hybrid P,E ligands of the type o-C₆H₄(CH₂PBut₂)(CH₂E) (E = PR₂, SR, S(O)But, NR₂, SiPh₂H) have been synthesised in two or three steps from the novel substrate, o-C₆H₄(CH₂PBut₂(BH₃)}(CH₂Cl). The initial step involved treatment of the substrate with the appropriate nucleophilic reagent, or preparation of a Grignard reagent from o-C₆H₄{CH₂PBut₂(BH₃)}(CH₂Cl) and reaction with the appropriate electrophile. In most cases, this versatile strategy produced air-stable crystalline ligand precursors. Phosphine deprotection was achieved via one of three methods, dependent upon the properties of the second functional group. The reactivity of three of these ligands — o-C₆H₄{CH₂PBut₂)(CH₂SBut) (14a), o-C₆H₄{CH₂PBut₂){CH₂S(O)But} (16) and o-C₆H₄(CH₂PBut₂)(CH₂NMe₂) (18a) — with Pt(II) and Pt(0) precursor complexes has been investigated. Chelated [PtCl₂(P,E)] complexes were synthesised with P,S ligand 14a and P,N ligand 18a, but attempts to produce the equivalent species with P,S=O ligand 16 were unsuccessful. The X-ray crystal structure of [PtCl₂(P,S)] complex 21 displayed an unexpectedly small ligand bite angle of 86.1°. A series of platinum(II) hydride complexes of the types [PtHL(P,S)₂] and [PtHL(P,S)₂]CH(SO₂CF₃)₂ (L = Cl¯, H¯, NCMe, −CH₂SBut , CO, pta) have been synthesised, where ligand 14a binds in a monodentate fashion through the phosphorus donor atom. This work has demonstrated the hemilability of ligand 14a, via the facile and reversible conversion between [PtH(κ¹P-14a)(κ²P,S-14a)]CH(SO₂CF₃)₂ (26) and [PtH(NCMe)(κ¹P-14a)₂]CH(SO₂CF₃)₂ (28). The X-ray crystal structure of [PtH₂(P,S)₂] complex 25 was used to calculate a cone angle of 180° for the phosphine moiety in ligand 14a. Reaction of P,S ligand 14a and P,S=O ligand 16 with [Pt(alkene)₃] complexes (alkene = ethene, norbornene) gave the chelated [Pt(alkene)(P,E)] complexes 32–35; however, under similar conditions a [Pt(norbornene)(P,N)] complex did not form. A large ligand bite angle of 106.6° was observed in the X-ray crystal structure of [Pt(norbornene)(P,S)] complex 34. Reaction of two equivalents of each of the P,E ligands with [Pt(norbornene)₃] gave the corresponding 14-electron linear complexes [Pt(P,E)₂] (36–38) with the ligands coordinated through the phosphorus donor atoms only. The reactivity of [Pt(norbornene)(P,S)] complex 34 and [Pt(P,S)₂] complex 36 has been investigated, resulting in the complexes [PtH{CH(SO₂CF₃)₂}(P,S)] (39), [Pt(norbornyl)(P,S)] (40), [Pt(ethyne)(P,S)] (41) and [Pt(O₂)(P,S)₂] (42). The reactivity of P,S ligand 14a was investigated with Pd(II) and Pd(0) precursors, resulting in the identification of five coordination modes of this ligand. Monodentate binding was observed in [Pd(P,S)₂] complex 44, and chelation in the [Pd(alkene)(P,S)] complexes 47 (alkene = norbornene) and 48 (alkene = dba). Reaction of ligand 14a with [PdCl₂(NCBut)₂] at raised temperature resulted in S−C bond cleavage and the formation of palladium dimer 43 with bidentate coordination of the ligand through phosphine and bridging thiolate moieties. Reaction of ligand 14a with [Pd(OAc)₂] resulted in C−H activation of the aryl backbone and formation of [Pd(μ-OAc)(P,C)]₂ dimer 46. In the presence of excess [Pd(OAc)₂], palladium hexamer 45 was formed, with a combination of P,C palladacycle and monodentate thioether binding resulting in bridging P,C,S coordination of ligand 14a. The Sonogashira cross-coupling of 4-bromoanisole and phenylethyne was performed with 3 mol% of a pre-catalyst mixture containing P,S ligand 14a, [Pd(OAc)₂] and CuI, resulting in quantitative conversion to 4-(phenylethynyl)anisole in four hours. Two enyne by-products were also identified from the reaction. Variations to the pre-catalyst mixture and catalyst loading indicated there was a significant ligand dependence on the yield and selectivity of the reactions. Mercury drop tests and dynamic light scattering experiments confirmed the presence of palladium nanoparticles in the reaction solution; however, the active catalytic species in these reactions has not been identified.</p>

scholarly journals Hybrid P,E Ligands: Synthesis, Coordination Chemistry and Catalysis

2021 ◽  
Author(s):  
◽  
Kathryn Mary Allan
Keyword(s):  
Crystal Structure ◽  
Bond Cleavage ◽  
Cone Angle ◽  
Initial Step ◽  
Catalyst Loading ◽  
Bidentate Coordination ◽  
X Ray ◽  
Coordination Modes ◽  
Bite Angle ◽  
Carbon Carbon Bond

<p>This thesis provides an account of research into a family of novel hybrid P,E ligands containing an o-xylene backbone. A methodology for the synthesis of these ligands has been developed, and their coordination behaviour with platinum(II) and platinum(0) precursors has been explored, with particular focus on a phosphinethioether (P,S) ligand of this type. The coordination modes of this P,S ligand with palladium precursors have also been investigated, and the utility of the ligand in a palladium and copper co-catalysed Sonogashira carbon-carbon bond-forming reaction has been evaluated. A range of hybrid P,E ligands of the type o-C₆H₄(CH₂PBut₂)(CH₂E) (E = PR₂, SR, S(O)But, NR₂, SiPh₂H) have been synthesised in two or three steps from the novel substrate, o-C₆H₄(CH₂PBut₂(BH₃)}(CH₂Cl). The initial step involved treatment of the substrate with the appropriate nucleophilic reagent, or preparation of a Grignard reagent from o-C₆H₄{CH₂PBut₂(BH₃)}(CH₂Cl) and reaction with the appropriate electrophile. In most cases, this versatile strategy produced air-stable crystalline ligand precursors. Phosphine deprotection was achieved via one of three methods, dependent upon the properties of the second functional group. The reactivity of three of these ligands — o-C₆H₄{CH₂PBut₂)(CH₂SBut) (14a), o-C₆H₄{CH₂PBut₂){CH₂S(O)But} (16) and o-C₆H₄(CH₂PBut₂)(CH₂NMe₂) (18a) — with Pt(II) and Pt(0) precursor complexes has been investigated. Chelated [PtCl₂(P,E)] complexes were synthesised with P,S ligand 14a and P,N ligand 18a, but attempts to produce the equivalent species with P,S=O ligand 16 were unsuccessful. The X-ray crystal structure of [PtCl₂(P,S)] complex 21 displayed an unexpectedly small ligand bite angle of 86.1°. A series of platinum(II) hydride complexes of the types [PtHL(P,S)₂] and [PtHL(P,S)₂]CH(SO₂CF₃)₂ (L = Cl¯, H¯, NCMe, −CH₂SBut , CO, pta) have been synthesised, where ligand 14a binds in a monodentate fashion through the phosphorus donor atom. This work has demonstrated the hemilability of ligand 14a, via the facile and reversible conversion between [PtH(κ¹P-14a)(κ²P,S-14a)]CH(SO₂CF₃)₂ (26) and [PtH(NCMe)(κ¹P-14a)₂]CH(SO₂CF₃)₂ (28). The X-ray crystal structure of [PtH₂(P,S)₂] complex 25 was used to calculate a cone angle of 180° for the phosphine moiety in ligand 14a. Reaction of P,S ligand 14a and P,S=O ligand 16 with [Pt(alkene)₃] complexes (alkene = ethene, norbornene) gave the chelated [Pt(alkene)(P,E)] complexes 32–35; however, under similar conditions a [Pt(norbornene)(P,N)] complex did not form. A large ligand bite angle of 106.6° was observed in the X-ray crystal structure of [Pt(norbornene)(P,S)] complex 34. Reaction of two equivalents of each of the P,E ligands with [Pt(norbornene)₃] gave the corresponding 14-electron linear complexes [Pt(P,E)₂] (36–38) with the ligands coordinated through the phosphorus donor atoms only. The reactivity of [Pt(norbornene)(P,S)] complex 34 and [Pt(P,S)₂] complex 36 has been investigated, resulting in the complexes [PtH{CH(SO₂CF₃)₂}(P,S)] (39), [Pt(norbornyl)(P,S)] (40), [Pt(ethyne)(P,S)] (41) and [Pt(O₂)(P,S)₂] (42). The reactivity of P,S ligand 14a was investigated with Pd(II) and Pd(0) precursors, resulting in the identification of five coordination modes of this ligand. Monodentate binding was observed in [Pd(P,S)₂] complex 44, and chelation in the [Pd(alkene)(P,S)] complexes 47 (alkene = norbornene) and 48 (alkene = dba). Reaction of ligand 14a with [PdCl₂(NCBut)₂] at raised temperature resulted in S−C bond cleavage and the formation of palladium dimer 43 with bidentate coordination of the ligand through phosphine and bridging thiolate moieties. Reaction of ligand 14a with [Pd(OAc)₂] resulted in C−H activation of the aryl backbone and formation of [Pd(μ-OAc)(P,C)]₂ dimer 46. In the presence of excess [Pd(OAc)₂], palladium hexamer 45 was formed, with a combination of P,C palladacycle and monodentate thioether binding resulting in bridging P,C,S coordination of ligand 14a. The Sonogashira cross-coupling of 4-bromoanisole and phenylethyne was performed with 3 mol% of a pre-catalyst mixture containing P,S ligand 14a, [Pd(OAc)₂] and CuI, resulting in quantitative conversion to 4-(phenylethynyl)anisole in four hours. Two enyne by-products were also identified from the reaction. Variations to the pre-catalyst mixture and catalyst loading indicated there was a significant ligand dependence on the yield and selectivity of the reactions. Mercury drop tests and dynamic light scattering experiments confirmed the presence of palladium nanoparticles in the reaction solution; however, the active catalytic species in these reactions has not been identified.</p>

Homonuclear PdII and PtII and heteronuclear PdII-AuI and PtII-AuI complexes of a tripod triphosphine ligand: synthesis, characterization and reactions with molecules of biological relevance

2000 ◽  
Vol 53 (8) ◽  
pp. 635 ◽  
Author(s):  
Paloma Sevillano ◽  
Abraha Habtemariam ◽  
M. Inés García Seijo ◽  
Alfonso Castiñeiras ◽  
Simon Parsons ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Mass Spectrometry ◽  
Partial Oxidation ◽  
Bond Cleavage ◽  
Planar Geometry ◽  
Conductivity Measurements ◽  
Initial Attack ◽  
X Ray ◽  
Square Planar ◽  
Linear Geometry

Complexes of the type Pd(tripod)X2 [tripod = MeC(CH2PPh2)3; X = Cl (1), Br (2), I (3)] and Pt(tripod)X2 [X = Cl (4), Br (5), I (6)] have been synthesized. In these complexes tripod acts as a bidentate chelating ligand. The uncoordinated phosphorus atom can bind to AuI to form the bimetallic complexes PdAu(tripod)X3 [X = Cl (7), Br (8), I (9)] and PtAu(tripod)X3 [X = Cl (10), Br (11), I (12)]. Complexes (1)–(12) have been characterized by microanalysis, f.a.b. mass spectrometry, i.r. spectroscopy, 31P and 195Pt n.m.r. spectroscopies, and conductivity measurements. The structures of complexes (1), (4) and (11), as well as that of the unusual complex Cl2Pt(tripod)AuBr0.5Cl0.5 (13), isolated from reaction of Pt(tripod)Br2 (5), and [Au(thiodiglycol)Cl], have been determined. All complexes show square-planar geometry for PdII or PtII and linear geometry for AuI. The X-ray crystal structure of (1) showed partial oxidation of the dangling phosphorus of the ligand in 50% of the molecule distributed randomly over the lattice. Reactions of complex (4), Pt(tripod)Cl2, with the tripeptide glutathione (GSH) showed the formation of [Pt2(tripod)2(GS-µ–S)2]2+ (15a). No reaction with N-acetyl-L-methionine (AcMet) or guanosine 5´-monophosphate (5´-GMP) was observed. Reactions of [Pt(tripod–O)(ONO2)2] (14) with GSH resulted in the formation of [Pt2(tripod–O)2(GS-µ-S)2]2+ (15b). Displacement of the S-containing molecules by 5´-GMP in the presence of AuI, via Pt–S bond cleavage, was observed for complex (15b). PtAu(tripod)Cl3 (10) reacted with GSH, with initial attack on the AuI centre.

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