Mixed Metal Acetylides: The PtII Aryl Acetylide “[PtC6H2(CH2NMe2)22,6-(C≡C)-4]” as a Connective Fragment

The meta-diaminoaryl ferrocenes Fc-NCN-H (3) and Fc-C"C-NCN-H (5) (Fc = (g 5 -C 5 H 5 )(g 5 -C 5 H 4 )Fe, NCN-H = C 6 H 3 (CH 2 NMe 2 ) 2 -3,5) can be used as precursors in the preparation of heterobimetallic transition metal complexes of structural type Fc-NCN-MX (NCN = [C 6 H 2 (CH 2 NMe 2 ) 2 -2,6] À ; MX = PdCl (7), PtCl (8), PtI (9)) and Fc-C"C-NCN-MX (MX = PdCl (11), PdI (12), PtCl (13)), respectively. They are accessible by applying different synthesis procedures, including oxidative addition and metallation-transmetallation processes.Cyclovoltammetric studies show that the ferrocene moieties in 3, 5, 7-9 and 11-13 can reversibly be oxidised. The potential of the Fe(II)/Fe(III) redox couple decreases with increasing electron density at the NCN pincer unit. The use of 8 as a possible (electro)chemical sensor in the detection of SO 2 is discussed as well.The solid-state structures of 8 and 13 are reported. The crystals of 8 contain two molecules of 8 in the asymmetric unit. The plane of the C 6 H 2 moiety is with 27.2(3)°and 38.2(3)°tilted towards the C 5 H 4 entity, while in 13 an angle of 45.9(3)°can be found. The d 8 -electron configured platinum atoms possess a somewhat distorted square-planar surrounding, setup by two Me 2 NCH 2 ortho-substituents, the NCN C ipso carbon atom and the chloride ligand.

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“…It most likely arises from the oxidation of the NCN pincer unit [9,11]. An analogous behaviour has been reported for benzyl amine [12].…”

Section: Electrochemical Studiessupporting

confidence: 65%

Heterobimetallic Fe–Pd and Fe–Pt NCN pincer complexes (NCN=[C6H2(CH2NMe2)2-2,6]−)

Köcher

Lutz

Spek

et al. 2006

Inorganica Chimica Acta

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“…Calc. for C 29 H 23 NP 2 S 2 : C,68.09;H,4.53;N,2.74;S,12.54. Found: C,67.90;H,4.73;N,2.89;S,12.12%.…”

Section: Synthesis Of 35-bis(diphenylphosphinothioyl)pyridine (1)mentioning

confidence: 99%

“…for C 29 H 22 INP 2 PdS 2 : C,46.82;H,2.98;N,1.88;S,8.62. Found: C,49.55;H,3.20;N,1.88;S,pyridinium-C 4 ,S,S 0 ] iodopalladium(II) iodide (3) To a THF (2 mL) solution of 2c (9.7 mg, 0.013 mmol) was added CH 3 I (1 mL) and refluxed for 6 h. The solvent was evaporated, and the residue was washed with CHCl 3 , acetone and water. The product was purified by recrystallization from a mixture of CH 3 CN and ether to give a yellow powder of 3 (7.4 mg, 64% yield).…”

Section: Synthesis Of [35-bis(diphenylphosphinothioyl)pyridine-c 4 mentioning

confidence: 99%

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Synthesis, structure, and quaternization and complexation reactions of κ3SCS pincer palladium complexes having 3,5-pyridinediyl unit

Meguro

Koizumi

Yamamoto

et al. 2008

Journal of Organometallic Chemistry

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“…7,8 Variable-temperature 1 H NMR experiments were carried out to study the dynamic aspects of the complexes. The AB patterns (6,8,9) and AA′ patterns (7,13) for the benzylic protons did not change in the temperature range 25-90°C. The signals for the NMe 2 groups of the NCN units of platinum complexes 6-9 did not show coalescence or line broadening at temperatures up to 90°C.…”

Section: Resultsmentioning

confidence: 86%

Structural Features and Dynamical Behavior of Heteroleptic trans-C,C-Bisaryl-Platinum(II) and -Palladium(II) Complexes

et al. 2005

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Several heteroleptic trans-bisaryl-Pt II complexes, trans-C,C-[Pt(NCN)R] (6-9), have been prepared starting from the readily available precursor [PtCl(NCN)] (1, NCN ) [C 6 H 3 (CH 2 -NMe 2 ) 2 -2,6] -) and ortho-substituted phenyl-or naphthyllithium reagents, respectively. Variable-temperature 1 H NMR spectroscopy shows that in solution the NCN ligand is η 3 -coordinated and that rotation of the trans-aryl ligand about the Pt-C ipso bond is slow or even nonexistent on the NMR time scale. Moreover, in the temperature range -80 to +90°C no dissociation of the Pt-N (NCN) coordination occurs. In contrast, the analogous Pd II complex 13 shows fluxional behavior of the nitrogen-to-metal coordination (above 0°C). The dynamic properties of this type of complexes can thus be tuned by the choice of metal. The crystal structure determinations of two trans-C,C-[M(NCN)(C 10 H 6 (CH 2 NMe 2 )-2)] complexes (8 (M ) Pt), 13 (M ) Pd)) are reported. The most significant feature in these structures is that the η 3 -N,C,N-coordinating NCN ligand present in 1 has been retained in 8 and 13; that is, the ortho-(dimethylamino)methyl group of the naphthyl ligand remains noncoordinating and cannot compete with the ortho-(dimethylamino)methyl groups of the NCN ligand.

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Mixed Metal Acetylides: The PtII Aryl Acetylide “[PtC6H2(CH2NMe2)22,6-(C≡C)-4]” as a Connective Fragment

Abstract: H 4 CN-4] have been prepared. Studies directed towards the coordinative properties of the C 2 unit of 1 have been carried out and heterotrimetallic [µ-(Me 3 SiCϵC{Pt}Cl][Co 2 (CO) 6 ] (10) could be synthesised. The

Cited by 40 publications

References 40 publications

Heterobimetallic Fe–Pd and Fe–Pt NCN pincer complexes (NCN=[C6H2(CH2NMe2)2-2,6]−)

Heterobimetallic Fe–Pd and Fe–Pt NCN pincer complexes (NCN=[C6H2(CH2NMe2)2-2,6]−)

Synthesis, structure, and quaternization and complexation reactions of κ3SCS pincer palladium complexes having 3,5-pyridinediyl unit

Structural Features and Dynamical Behavior of Heteroleptic trans-C,C-Bisaryl-Platinum(II) and -Palladium(II) Complexes

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