Tertiary phosphine adducts of manganese(II) dialkyls. Part 1. Synthesis, properties and structures of alkyl-bridged dimers

Howard, Christopher G.; Wilkinson, Geoffrey; Thornton‐Pett, Mark; Hursthouse, Michael B.

doi:10.1039/dt9830002025

Cited by 46 publications

(21 citation statements)

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“…The structure revealed a four-coordinate manganese center with a distorted tetrahedral environmental (τ = 0.73). The Mn(1)-C(1) bond distance of 2.146(2) Å is comparable with the values reported for similar compounds Mn 2 (CH 2 Ph) 4 (PMe 3 ) 2 (2.127(3) Å) 40…”

Section: Dalton Transactions Papersupporting

confidence: 86%

Synthesis and characterization of coordinatively unsaturated nickel(ii) and manganese(ii) alkyl complexes supported by the hydrotris(3-phenyl-5-methylpyrazolyl)borate (TpPh,Me) ligand

et al. 2013

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The synthesis of several nickel(II) and manganese(II) alkyl complexes supported by hydrotris(3-phenyl-5-methylpyrazolyl)borate (Tp(Ph,Me)) ligand is reported. The metal halide complexes Tp(Ph,Me)MnCl(CH3CN) (1) and Tp(Ph,Me)NiCl (4) were used as precursors for synthesis of Tp(Ph,Me)MnCH2Si(Me)3 (2), Tp(Ph,Me)MnCH2Ph (3), Tp(Ph,Me)NiCH2Si(Me)3 (5) and Tp(Ph,Me)NiCH2Ph (6). The resulting Mn(II) and Ni(II) alkyl complexes, 2-3 and 5-6, were characterized by X-ray crystallography, NMR spectroscopy, and FT-IR spectroscopy. X-ray crystallographic analysis revealed distorted tetrahedral geometries for complexes 2-3 and 5 with a κ(3)-Tp(Ph,Me). Complex 6, on the other hand, was found to have a distorted square planar geometry with κ(2)-Tp(Ph,Me) and an η(3)-benzyl ligand. Transformations of 4 and Tp(Ph,Me)CoCl (10) via treatment with NaN3 to yield Tp(Ph,Me)NiN3 (11), Tp(Ph,Me)CoN3 (12), along with the synthesis of (Tp(Ph,Me))2Ni (8) and Tp(Ph,Me)NiCl(3-Ph-5MepzH) (9) are also reported.

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Section: Dalton Transactions Papersupporting

confidence: 86%

Synthesis and characterization of coordinatively unsaturated nickel(ii) and manganese(ii) alkyl complexes supported by the hydrotris(3-phenyl-5-methylpyrazolyl)borate (TpPh,Me) ligand

et al. 2013

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“…Despite the popularity of neopentyl as a sterically demanding alkyl ligand for transition-metal complexes, few examples of species with bridging neopentyl groups have been reported. − Notably, a handful of dimanganese complexes have been shown to support bridging neopentyl groups, generally with Mn···Mn distances between 2.685 and 2.718 Å, Mn–C bridge distances between 2.185 and 2.645 Å, and ∠Mn1–C bridge –Mn2 angles between 69.6 and 72.7°. − While the metal–metal and metal–carbon distances observed in these dimanganese complexes are significantly longer than those observed in 3 , the metal–carbon–metal angles are quite similar.…”

Section: Dicopper Alkyl Complexesmentioning

confidence: 99%

Dicopper Alkyl Complexes: Synthesis, Structure, and Unexpected Persistence

et al. 2018

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Cationic μ-alkyl dicopper complexes [Cu2(μ-η 1 :η 1 -R)DPFN]NTf2 (R = CH3, CH2CH3, CH2C(CH3)3; DPFN = 2,7-bis(fluorodi(2-pyridyl)-methyl)-1,8-naphthyridine; NTf2 -= N(SO2CF3)2 -) were synthesized by treatment of an acetonitrile-bridged dicopper complex [Cu2(μ-η 1 :η 1 -NCCH3)DPFN](NTf2)2 with LiR or MgR2. Structural characterization by X-ray crystallography and NMR spectroscopy revealed that the alkyl ligands symmetrically bridge the two copper centers, and the complexes persist in room temperature solution. Notably, the μ-methyl complex showed less than 20% decomposition after 34 days in room temperature THF solution. Treatment of the μ-methyl complex with acids allows installation of a range of monoanionic bridging ligands. However, surprisingly insertion into the dicopper-carbon bond was not observed upon addition of a variety of reagents, suggesting that these complexes exhibit a fundamentally new reactivity profile for alkylcopper species. Electrochemical characterization revealed oxidation-reduction events that evidence putative mixed-valence dicopper alkyl complexes. Computational studies suggest that the dicopper-carbon bonds are highly covalent, possibly explaining their remarkable stability.

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“…counter ions. 20 Several Lewis base complexes, such as MnPh 2 {P(C 6 H 11 ) 3 }, 21 Mn(CH 2 SiMe 3 ) 2 (PR 3 ) (R 3 = Et 3 or Me 2 Ph), 22 Mn 2 R 4 (PMe 3 ) 2 (R = CH 2 SiMe 3 , CH 2 t Bu, or CH 2 Ph), 22 Mn(C 6 F 5 ) 2 (THF) 2 , 23 Mn(C 6 F 5 ) 2 (dme) (dme = 1, 2-dimethoxyethane), 23 and {Mn(THF)(Mes)(m-Mes)} 2 24 are also known. In sharp contrast, well characterized heteroleptic derivatives of the type Mn(X)R (X = halide or other heteroatom centered group; R = alkyl or aryl, manganese analogues of Grignard reagents), MnRR¢ (R, R¢ = different organic groups) or ionic species of the general formula [MnR n R¢ m ] -(n+m-2) or [MnR n X m ] -(n+m-2) (n, m = 1, 2, or 3) are much scarcer.…”

Section: Introductionmentioning

confidence: 99%

Terphenyl substituted derivatives of manganese(ii): distorted geometries and resistance to elimination

Fettinger

Long

et al. 2010

Dalton Trans.

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Reaction of {Li(THF)Ar'MnI(2)}(2) (Ar' = C(6)H(3)-2,6-(C(6)H(2)-2,6-(i)Pr(3))(2)) with LiAr', LiC≡CR (R = (t)Bu or Ph), or (C(6)H(2)-2,4,6-(i)Pr(3))MgBr(THF)(2) afforded the diaryl MnAr'(2) (1), the alkynyl salts Ar'Mn(C≡C(t)Bu)(4){Li(THF)}(3) (2) and Ar'Mn(C≡CPh)(3)Li(3)(THF)(Et(2)O)(2)(μ(3)-I) (3), and the manganate salt {Li(THF)}Ar'Mn(μ-I)(C(6)H(2)-2,4,6-(i)Pr(3)) (4), respectively. Complex 4 reacted with one equivalent of (C(6)H(2)-2,4,6-(i)Pr(3))MgBr(THF)(2) to afford the homoleptic dimer {Mn(C(6)H(2)-2,4,6-(i)Pr(3))(μ-C(6)H(2)-2,4,6-(i)Pr(3))}(2) (5), which resulted from the displacement of the bulkier Ar' ligand in preference to the halogen. The reaction of the more crowded {Li(THF)Ar*MnI(2)}(2) (Ar* = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-(i)Pr(3))(2)) with Li(t)Bu gave complex Ar*Mn(t)Bu (6). Complex 1 is a rare monomeric homoleptic two-coordinate diaryl Mn(II) complex; while 6 displays no tendency to eliminate β-hydrogens from the (t)Bu group because of the stabilization supplied by Ar*. Compounds 2 and 3 have cubane frameworks, which are constructed from a manganese, three carbons from three acetylide ligands, three lithiums, each coordinated by a donor, plus either a carbon from a further acetylide ligand (2) or an iodide (3). The Mn(II) atom in 4 has an unusual distorted T-shaped geometry while the dimeric 5 features trigonal planar manganese coordination. The chloride substituted complex Li(2)(THF)(3){Ar'MnCl(2)}(2) (7), which has a structure very similar to that of {Li(THF)Ar'MnI(2)}(2), was also prepared for use as a possible starting material. However, its generally lower solubility rendered it less useful than the iodo salt. Complexes 1-7 were characterized by X-ray crystallography and UV-vis spectroscopy. Magnetic studies of 2-4 and 6 showed that they have 3d(5) high-spin configurations.

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Tertiary phosphine adducts of manganese(II) dialkyls. Part 1. Synthesis, properties and structures of alkyl-bridged dimers

Abstract: The reactions of manganese(i1) dialkyls with tertiary phosphines or of MnCI, with magnesium dialkyls in the presence of phosphines leads to dimeric complexes of

Cited by 46 publications

References 1 publication

Synthesis and characterization of coordinatively unsaturated nickel(ii) and manganese(ii) alkyl complexes supported by the hydrotris(3-phenyl-5-methylpyrazolyl)borate (TpPh,Me) ligand

Synthesis and characterization of coordinatively unsaturated nickel(ii) and manganese(ii) alkyl complexes supported by the hydrotris(3-phenyl-5-methylpyrazolyl)borate (TpPh,Me) ligand

Dicopper Alkyl Complexes: Synthesis, Structure, and Unexpected Persistence

Terphenyl substituted derivatives of manganese(ii): distorted geometries and resistance to elimination

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