New Ruthenium(II) Complexes of Functionalized Monoanionic Aryldiamine N,C,N'‐Terdentate Ligands: Syntheses of [RuII{2,6‐(Me2NCH2)2‐4‐R‐C6H2}‐(terpy)]+Cl‐; X‐ray Structure of a Dimeric Organolithium Compound, [Li{2,6‐(Me2NCH2)2‐4‐Ph‐C6H2}]2

Steenwinkel, Pablo; James, Stuart L.; Grove, David M.; Veldman, Nora; Spek, Anthony L.; Koten, Gerard van

doi:10.1002/chem.19960021117

Cited by 77 publications

(62 citation statements)

References 25 publications

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“…The procedure started from 1-bromo-3,5-bis[(dimethylamino)methyl]benzene (1, Br-(NC(H)N)) [9], which was converted into the respective phosphanes 2 and 4 via lithium-bromide exchange followed by reaction with chlorodiphenylphosphane or phosphorus tribromide (Scheme 1). In the case of 2, the crude product was obtained as a yellow oil, which could be purified by bulb-to-bulb distillation, affording the pure phosphane as a dark yellow oil in a yield of 71%.…”

Section: Preparative Resultsmentioning

confidence: 99%

Synthesis, coordination chemistry, and metal complex reactivity of (dimethylamino)methyl-substituted triarylphosphanes; X-ray study on [AuCl(PPh3−nArn)] (Ar=1-C6H3(CH2NMe2)2-3,5, n=1, 3; Ar=1-C6H4(CH2NMe2)-4, n=3)

Kreiter

Firet

Ruts

et al. 2006

Journal of Organometallic Chemistry

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The synthesis of the first series of 4-mono and 3,5-bis(dimethylamino)methyl-functionalized triarylphosphanes of the general formula PPh 3 À n Ar n (Ar = 1-C 6 H 3 (CH 2 NMe 2 ) 2 -3,5 (NC(H)N), n = 1 (ligand 2) or n = 3 (ligand 4); Ar = 1-C 6 H 4 (CH 2 NMe 2 )-4 (NC(H)), n = 3 (ligand 7)) is described. These phosphanes were used for the construction of complexes of the form [AuCl(P)] and [PtCl 2 (P) 2 ]. In these complexes selective coordination of phosphorus to the metal ion is observed. The 31 P NMR data show the formation of cis-Pt complexes, even in the case of triarylphosphane 4, which features a tris{3,5-bis(dimethylamino)methyl} substitution pattern. The structure of the gold complex of mono-3,5-functionalized triarylphosphane 2 in the solid state shows a striking resemblance to the structure of the corresponding complex [AuCl(PPh 3 )]. The solid-state structure of the AuCl complex of tris-4-functionalized ligand 7 differs from that of [AuCl(PPh 3 )] in the sign of the torsion angles. The amine functionalities in this class of gold compounds could be reacted selectively with either acid (HCl, H 3 PO 4 ) to generate ammonium salts or with an alkylating agent (benzyl bromide) to afford benzyl ammonium salts, without the violation of the Au-P bond.

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Section: Preparative Resultsmentioning

confidence: 99%

Synthesis, coordination chemistry, and metal complex reactivity of (dimethylamino)methyl-substituted triarylphosphanes; X-ray study on [AuCl(PPh3−nArn)] (Ar=1-C6H3(CH2NMe2)2-3,5, n=1, 3; Ar=1-C6H4(CH2NMe2)-4, n=3)

Kreiter

Firet

Ruts

et al. 2006

Journal of Organometallic Chemistry

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“…[LiC 6 H 3 (CH 2 NMe 2 ) 2 -2,6] 2 was prepared according to the literature procedures [23]. Commercial anhydrous SnCl 4 , n-BuSnCl 3 , n-Bu 2 SnCl 2 and n-Bu 3 SnCl were used as supplied.…”

Section: General Commentsmentioning

confidence: 99%

Synthesis of novel terdentate N,C,N′-coordinated butyltin(IV) complexes and their redistribution reactions with SnCl4

Thoonen

Hoek

Wolf

et al. 2006

Journal of Organometallic Chemistry

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The Sn(IV) butyl complexes [Bu n SnCl 3 À n (NCN)] (NCN = [C 6 H 3 (CH 2 NMe 2 ) 2 -2,6] À , n = 1 (1), 2 (2), 3 (3)) were prepared. Spectroscopic analysis of 1-3 by 1 H and 119 Sn NMR gave evidence for the presence of intramolecular N ! Sn interactions in solution. The molecular structure of 1, as determined by a single-crystal X-ray diffraction study, revealed that it contained a six-coordinate Sn ( À or [SnCl 4 (aryl)] À stannate anion, respectively, with in each case one coordinated ortho-amine function and one protonated amine moiety involved in N-HÁ Á ÁCl-Sn hydrogen bonding in both compounds (2.14 Å for 6 and 2.18 Å for 8).

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“…Z-NCN pincer ligands (Z = para-substituent; 6: Z = I; [31] 7: Z = Ph [54] ), NCN-pincer complex [PtCl(Z-NCN)] (1: Z = H), [55] and their ruthenated derivatives [2](PF 6 ) and [3](BF 4 ) [27] were prepared according to literature procedures. 1,3-(Me 2 NCH 2 ) 2 C 6 H 4 was prepared as follows: α,αЈ-dibromoxylene (5 g, 19 mmol) was dissolved in dichloromethane (100 mL) and cooled to 0°C.…”

Section: Resultsmentioning

confidence: 99%

Ruthenium‐to‐Platinum Interactions in η⁶,η¹ NCN‐Pincer Arene Heterobimetallic Complexes: An Experimental and Theoretical Study

et al. 2010

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A series of η6,η1‐heterobimetallic complexes have been prepared in which a [Ru(η6‐arene)(C5R5)]+ fragment (R = H or Me) and an η1‐NCN‐pincer platinum fragment are combined within the same molecule. In complexes [2]+ and [3]+, the ruthenium and platinum centers are η6 and η1 coordinated, respectively, to the same arene ring, whereas in [4A]+ and [5A]+ they are coordinated to two different arene rings that are linked with a covalent bond ([4A]+) or an ethyl bridge ([5A]+). Upon changing the organic manifold between both metal centers, very strong ([2]+) to very weak ([5A]+) ruthenium‐to‐platinum interactions are obtained. Experimentally, X‐ray crystal structures show an increaing steric hindrance when the Ru–Pt distance diminishes, and electrochemical and 195Pt NMR spectroscopic studies show a decreasing electron density on platinum from [5A]+ to [2]+. Theoretical DFT calculations were undertaken, which show an increasing charge on platinum from [5A]+ to [2]+. Our theoretical analysis shows that the particularly strong ruthenium‐to‐platinum electronic interactions in [2]+ and [3]+ do not come from binding of ruthenium to platinum, but from the pincer Cipso sharing its electron density between both metal centers, which decreases the σ donation to platinum, and from increased backdonation of the platinum d electrons into the π system of the arene ring.

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New Ruthenium(II) Complexes of Functionalized Monoanionic Aryldiamine N,C,N'‐Terdentate Ligands: Syntheses of [Ru^II{2,6‐(Me₂NCH₂)₂‐4‐R‐C₆H₂}‐(terpy)]⁺Cl^‐; X‐ray Structure of a Dimeric Organolithium Compound, [Li{2,6‐(Me₂NCH₂)₂‐4‐Ph‐C₆H₂}]₂

Abstract: The new anionic functionalized

Cited by 77 publications

References 25 publications

Synthesis, coordination chemistry, and metal complex reactivity of (dimethylamino)methyl-substituted triarylphosphanes; X-ray study on [AuCl(PPh3−nArn)] (Ar=1-C6H3(CH2NMe2)2-3,5, n=1, 3; Ar=1-C6H4(CH2NMe2)-4, n=3)

Synthesis, coordination chemistry, and metal complex reactivity of (dimethylamino)methyl-substituted triarylphosphanes; X-ray study on [AuCl(PPh3−nArn)] (Ar=1-C6H3(CH2NMe2)2-3,5, n=1, 3; Ar=1-C6H4(CH2NMe2)-4, n=3)

Synthesis of novel terdentate N,C,N′-coordinated butyltin(IV) complexes and their redistribution reactions with SnCl4

Ruthenium‐to‐Platinum Interactions in η⁶,η¹ NCN‐Pincer Arene Heterobimetallic Complexes: An Experimental and Theoretical Study

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New Ruthenium(II) Complexes of Functionalized Monoanionic Aryldiamine N,C,N'‐Terdentate Ligands: Syntheses of [RuII{2,6‐(Me2NCH2)2‐4‐R‐C6H2}‐(terpy)]+Cl‐; X‐ray Structure of a Dimeric Organolithium Compound, [Li{2,6‐(Me2NCH2)2‐4‐Ph‐C6H2}]2

Abstract: The new anionic functionalized

Cited by 77 publications

References 25 publications

Synthesis, coordination chemistry, and metal complex reactivity of (dimethylamino)methyl-substituted triarylphosphanes; X-ray study on [AuCl(PPh3−nArn)] (Ar=1-C6H3(CH2NMe2)2-3,5, n=1, 3; Ar=1-C6H4(CH2NMe2)-4, n=3)

Synthesis, coordination chemistry, and metal complex reactivity of (dimethylamino)methyl-substituted triarylphosphanes; X-ray study on [AuCl(PPh3−nArn)] (Ar=1-C6H3(CH2NMe2)2-3,5, n=1, 3; Ar=1-C6H4(CH2NMe2)-4, n=3)

Synthesis of novel terdentate N,C,N′-coordinated butyltin(IV) complexes and their redistribution reactions with SnCl4

Ruthenium‐to‐Platinum Interactions in η6,η1 NCN‐Pincer Arene Heterobimetallic Complexes: An Experimental and Theoretical Study

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New Ruthenium(II) Complexes of Functionalized Monoanionic Aryldiamine N,C,N'‐Terdentate Ligands: Syntheses of [Ru^II{2,6‐(Me₂NCH₂)₂‐4‐R‐C₆H₂}‐(terpy)]⁺Cl^‐; X‐ray Structure of a Dimeric Organolithium Compound, [Li{2,6‐(Me₂NCH₂)₂‐4‐Ph‐C₆H₂}]₂

Ruthenium‐to‐Platinum Interactions in η⁶,η¹ NCN‐Pincer Arene Heterobimetallic Complexes: An Experimental and Theoretical Study