Ortho-chelated arylrhodium(I) complexes. X-ray structure of RhI[C6H3(CH2NMe2)2-o,o'-C,N](COD)

Koten, Gerard van; Zeijden, A. A. H. Van Der; Nordemann, R.A.; Kojić‐Prodić, Biserka; Spek, A.L.

doi:10.1021/om00099a010

Cited by 52 publications

(34 citation statements)

References 1 publication

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“…1, vide [15]. Like closely related [Me 2 SnBr(NCN)] [16], 2 is expected to be present as a five-coordinate species in which the aryl moiety only serves as a bidentate C,N-coordinated ligand. The fluxionality of the CH 2 NMe 2 substituents in such complexes has been demonstrated for several NCNpincer metal complexes [7a,16,17].…”

Section: Synthesis and Spectroscopic Analysis Of (Ncn)sn(iv)-butyl Comentioning

confidence: 98%

“…Like closely related [Me 2 SnBr(NCN)] [16], 2 is expected to be present as a five-coordinate species in which the aryl moiety only serves as a bidentate C,N-coordinated ligand. The fluxionality of the CH 2 NMe 2 substituents in such complexes has been demonstrated for several NCNpincer metal complexes [7a,16,17]. At room temperature, the 1 H NMR spectrum of the NCN-pincer ligand of 2 displayed only one set of singlet CH 2 and NMe 2 resonances, (d À86.9) [5c].…”

Section: Synthesis and Spectroscopic Analysis Of (Ncn)sn(iv)-butyl Comentioning

confidence: 99%

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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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Section: Synthesis and Spectroscopic Analysis Of (Ncn)sn(iv)-butyl Comentioning

confidence: 98%

Section: Synthesis and Spectroscopic Analysis Of (Ncn)sn(iv)-butyl Comentioning

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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“…Analytical data have been published elsewhere. [56] Compound 8: nBuLi (1.4 mL, 2.2 mmol) was added to a solution of the ligand 7 (601 mg, 2.2 mmol) in dry pentane (20 mL) at -78°C. After the addition was completed, the temperature was allowed to rise to room temperature and stirring was continued for 16 h. Subsequently, pentane was evaporated and replaced by dry ethyl ether (20 mL), then [PtCl 2 (SEt 2 ) 2 ] (999 mg, 2.2 mmol) was added as a solid under a flow of nitrogen, and the resulting suspension was stirred at room temperature for 24 h. Technical-grade diethyl ether was added, the suspension centrifuged, the ethereal layer decanted, and the crude solid reprecipitated from dichloromethane and pentane to afford 769 mg of a colored product.…”

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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“…The olefinic cod protons afford three complex and fairly broad multiplet resonances, one of which has double intensity, as a consequence of two protons having accidentally coincident chemical shifts. Based on the similarity of the 'H and 13C NMR spectroscopic features of 1 to those of Rh(C,H3CHZ-NMe,-2-R-6-C,NXcod) (R = H, Me, CH,NMe,) containing related achiral ligand systems [12], we suggest that 1 is isostructural with those complexes, i.e. it has a square-planar structure, as shown schematically in eqn.…”

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confidence: 87%

“…Surprisingly, the reaction of [RhCl(cod)], with an excess of Li(C,H,CH,NMe,-2-C,N), under the same conditions as described for 3-8 in Experimental details, affords the transmetallation product Rh(C,H,-CH,NMe,-2-C,NXcod) [12] as the only isolable product; addition of further Li(C,H,CH,NMe,-2-C,N) does not change the result. However, when the reaction mixture is agitated in an ultrasonic bath the rhodate complex Li(C,H,CH,NMe,-2-C,N),Rh(cod) (2) is obtained quantitatively.…”

Section: Synthesis and Stability Of The -Ate Complexes 2-8mentioning

confidence: 99%

Novel rhodate and iridate complexes containing C,N chelating arylamine ligand systems

Wehman-Ooyevaar

Vedral

Jastrzebski

et al. 1993

Journal of Organometallic Chemistry

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The synthesis is described of a series of new iridate and rhodate complexes Li(L-C,N),M(cod) (M = Rh, Ir; cod = cycloocta-1,5-diene) containing the orrho-chelating, mono-anionic, arylamine ligands L = C,H,CH,NR,-2 (R = Me, Et), C,H&H,NMe,-2-Me-5, C,H,CH(Me)NMe,-(R)-2 or C,H,CH,NMe('Bu)-2. The synthetic procedure for the -ate complexes from [MCl(cod& depends on the solubility of the starting aryllithium compound in benzene-an indirect effect of the bulky organic group on the N-donor atom. All the -ate complexes are formed diastereoselectively (and in the case of C,H,CH(Me)NMe,_(R)-2, enantioselectively). 'H and 13C NMR spectroscopies show the -ate complexes to be monomeric, heterobimetallic species. The 13C NMR data show clearly that CipsO is bridging between the late transition metal and the lithium centre. Consequbntly, this Cipso atom is chiral, and its configuration is stabilized by intramolecular coordination of the N-donor atom of the o&o-amine substituent. The -ate complexes are fluxional with differences in fluxionality (which involve N-dissociation/association, pyramidal inversion at N and rotation around the C,,,-N bond) that can be attributed to differences in the bulk of the groups on the nitrogen atom.

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Ortho-chelated arylrhodium(I) complexes. X-ray structure of RhI[C6H3(CH2NMe2)2-o,o'-C,N](COD)

Cited by 52 publications

References 1 publication

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

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

Novel rhodate and iridate complexes containing C,N chelating arylamine ligand systems

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Ortho-chelated arylrhodium(I) complexes. X-ray structure of RhI[C6H3(CH2NMe2)2-o,o'-C,N](COD)

Cited by 52 publications

References 1 publication

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

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

Novel rhodate and iridate complexes containing C,N chelating arylamine ligand systems

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Product

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