Mn(CO)<sub>2</sub> Complexes of Cyclopentadienyl/Scorpionate Hybrid Ligands

Kunz, Kerstin; Vitze, Hannes; Bolte, Michael; Lerner, and Hans-Wolfram

doi:10.1021/om700450j

Cited by 29 publications

(23 citation statements)

References 49 publications

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“…NMe 2 Et was dried over neat solid n -BuLi (6 h) and then vacuum-transferred to a Schlenk storage vessel. Ferrocene (FcH), cymantrene (CymH), and BBr 3 are commercially available; (C 5 Me 5 )Fe(C 5 H 5 ) (Fc # H), FcBBr 2 ( F ), ,, and CymBBr 2 ( 6 ) , can be synthesized according to literature procedures.…”

Section: Methodsmentioning

confidence: 99%

Reactivity of [(C₅Me₅)Fe(C₅H₄BBr₂)] and [(OC)₃Mn(C₅H₄BBr₂)] toward Et₃SiH: Facile Access to [(OC)₃Mn(C₅H₄BH₂)]₂ and to Boron-Bridged Dinuclear Organometallics

et al. 2010

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The reaction of Fc # BBr 2 with 2 equiv of Et 3 SiH gives the boron-bridged dinuclear species Fc # 2 BBr with concomitant liberation of B 2 H 6 (Fc # = (C 5 Me 5 )Fe(C 5 H 4 )). The transformation is slow (48 h) but nevertheless provides yields of >85%. Fc # 2 BBr can conveniently be converted into the aminoborane Fc # 2 BNMe 2 by treatment with Me 3 SiNMe 2 . For an X-ray crystal structure analysis, Fc # 2 BNMe 2 was hydrolyzed to the borinic acid Fc # 2 BOH. A cross-coupling experiment using Et 3 SiH and an equimolar mixture of FcBBr 2 and Fc # BBr 2 led to the formation of the mixed product Fc(Fc # )BBr with high selectivity (Fc = (C 5 H 5 )Fe(C 5 H 4 )). Similar to the case for Fc # 2 BBr, Cym 2 BBr can be prepared from CymBBr 2 and Et 3 SiH (Cym = (OC) 3 Mn(C 5 H 4 )). In contrast to FcBH 2 , which exists only as transient intermediate on the way to Fc 2 BH, CymBH 2 is an isolable species. The compound was synthesized from a concentrated toluene solution of CymBBr 2 and excess neat Et 3 SiH at -78 °C and forms B-H-B-bridged dimers (CymBH 2 ) 2 in the solid state (X-ray crystallography). Our reactivity studies indicate that the Et 3 SiH-induced coupling reaction of derivatives L n M-(C 5 H 4 BBr 2 ) is fastest for electron-rich cyclopentadienyl complexes. Addition of NMe 2 Et to (CymBH 2 ) 2 affords the monomeric amine adduct CymBH 2 (NMe 2 Et). The reaction of (CymBH 2 ) 2 with HCC t Bu in a stoichiometric ratio of 1:4 (or slightly higher) results in a mixture of products from which the dinuclear hydroboration product (CymB(C(H)dC(H) t Bu)) 2 C(H)-C(H) 2 t Bu could be isolated and structurally characterized. To obtain the divinylborane CymB(C(H)dC(H) t Bu) 2 in high yield and pure form, (CymBH 2 ) 2 has to be dissolved in excess neat HCC t Bu.

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Section: Methodsmentioning

confidence: 99%

Reactivity of [(C₅Me₅)Fe(C₅H₄BBr₂)] and [(OC)₃Mn(C₅H₄BBr₂)] toward Et₃SiH: Facile Access to [(OC)₃Mn(C₅H₄BH₂)]₂ and to Boron-Bridged Dinuclear Organometallics

et al. 2010

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“…A closer inspection of the solid state structure suggests, however, a counterion effect as the likely explanation, because the K + cation in crystalline K [11] is pcoordinated to two pyrazolyl rings, [30,31,47,68] one from each scorpionate ligand. Such a type of molecular pocket is only Figure 11.…”

Section: Quantum Chemical Calculationsmentioning

confidence: 99%

Copper Complexes of Mono‐ and Ditopic [(Methylthio)methyl]borates: Missing Links and Linked Systems En Route to Copper Enzyme Models

Ruth

Tüllmann

Vitze

et al. 2008

Chemistry A European J

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TMEDA-free (TMEDA: tetramethylethylenediamine) LiCH(2)SMe is a suitable reagent for the selective introduction of (methylthio)methyl groups into PhBBr(2) and its p-silylated derivative Me(3)Si--C(6)H(4)--BBr(2). The resulting compounds, R*--C(6)H(4)--B(Br)(CH(2)SMe) (R*=H: 2; R*=SiMe(3): 7) and PhB(CH(2)SMe)(2) (3), form cyclic dimers through B--S adduct bonds in solution and in the solid state. Compounds 2 and 3 have successfully been used for preparing the (N(2)S) scorpionate [PhBpz(2)(CH(2)SMe)](-) ([5](-)) (pz: pyrazol-1-yl) and the (NS(2)) scorpionate [PhBpz(CH(2)SMe)(2)](-), respectively. Compound 7 proved to be an excellent building block for the heteroditopic poly(pyrazol-1-yl)borate p-[pz(3)B--C(6)H(4)--Bpz(2)(CH(2)SMe)](2-) ([10](2-)) that mimics the two ligation sites of the copper enzymes peptidylglycine alpha-hydroxylating monooxygenase and dopamine beta-monooxygenase. Treatment of the monotopic tripod [5](-) with CuCl and CuBr(2) results in the formation of complexes K[Cu(5)(2)] and [Cu(5)(2)]. An X-ray crystallography study of K[Cu(5)(2)] revealed a tetrahedral (N(2)S(2)) coordination environment for the Cu(I) ion, whereas the Cu(II) ion of [Cu(5)(2)] possesses a square-pyramidal (N(4)S) ligand sphere (S-atom in the axial position). The remarkable redox properties of K[Cu(5)(2)] and [Cu(5)(2)] have been assessed by cyclic voltammetry and quantum chemical calculations. The reaction of K[Cu(5)(2)] with dry air leads to the Cu(II) species [Cu(5)(2)] and to a tetranuclear Cu(II) complex featuring [PhB(O)pz(2)](2-) ligands. Addition of CuCl to K(2)[10] gives the complex K(3)[Cu(10)(2)] containing two ligand molecules per Cu(I) center. The Cu(I) ion binds to both heteroscorpionate moieties and thereby establishes a coordination environment similar to that of the Cu(I) ion in K[Cu(5)(2)].

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“…The vast majority of tris(pyrazol‐1‐yl)borates still contains a hydrogen atom as substituent R. In some cases, alkyl and aryl substituents (e.g., R = Me, i Pr, n Bu, Ph), have been used, mainly to avoid complications from possible reactions of the BH fragment and to ensure good solubility of the complexes obtained. Moreover, the R group offers the possibility to link two scorpionate moieties together and, thereby, generate oligotopic ligands for the preparation of coordination polymers,, , metal‐containing macrocycles, and multiple‐decker sandwich complexes . Recently, Reger et al elucidated the spin‐state crossover behavior of a series of Fe II complexes [(RBpz 3 ) 2 Fe] (R = substituted aryl) in the solid state.…”

Section: Introductionmentioning

confidence: 99%

Third‐Generation Scorpionates [RBpz3]– – How Influential Is the Nondonor Substituent R?

2015

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Five pairs of perfluorophenyl-and phenyl-substituted tris(pyrazol-1-yl)borate complexes have been prepared and thoroughly investigated, namely, [(C 6 R′ 5 Bpz 3 ) 2 Fe], [(C 6 R′ 5 Bpz 3 ) 2 Cu], [(C 6 R′ 5 Bpz 3 )Mn(CO) 3 ], K[(C 6 R′ 5 Bpz 3 )Mo(CO) 3 ], and [(C 6 R′ 5 Bpz 3 )Mo(CO) 2 (2-methallyl)] (R′ = F, H; pz = pyrazol-1yl). X-ray crystal structure analyses and IR spectroscopical measurements reveal only a minor influence of the spectator substit- [a]

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Mn(CO)₂ Complexes of Cyclopentadienyl/Scorpionate Hybrid Ligands

Cited by 29 publications

References 49 publications

Reactivity of [(C₅Me₅)Fe(C₅H₄BBr₂)] and [(OC)₃Mn(C₅H₄BBr₂)] toward Et₃SiH: Facile Access to [(OC)₃Mn(C₅H₄BH₂)]₂ and to Boron-Bridged Dinuclear Organometallics

Reactivity of [(C₅Me₅)Fe(C₅H₄BBr₂)] and [(OC)₃Mn(C₅H₄BBr₂)] toward Et₃SiH: Facile Access to [(OC)₃Mn(C₅H₄BH₂)]₂ and to Boron-Bridged Dinuclear Organometallics

Copper Complexes of Mono‐ and Ditopic [(Methylthio)methyl]borates: Missing Links and Linked Systems En Route to Copper Enzyme Models

Third‐Generation Scorpionates [RBpz3]– – How Influential Is the Nondonor Substituent R?

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Mn(CO)2 Complexes of Cyclopentadienyl/Scorpionate Hybrid Ligands

Cited by 29 publications

References 49 publications

Reactivity of [(C5Me5)Fe(C5H4BBr2)] and [(OC)3Mn(C5H4BBr2)] toward Et3SiH: Facile Access to [(OC)3Mn(C5H4BH2)]2 and to Boron-Bridged Dinuclear Organometallics

Reactivity of [(C5Me5)Fe(C5H4BBr2)] and [(OC)3Mn(C5H4BBr2)] toward Et3SiH: Facile Access to [(OC)3Mn(C5H4BH2)]2 and to Boron-Bridged Dinuclear Organometallics

Copper Complexes of Mono‐ and Ditopic [(Methylthio)methyl]borates: Missing Links and Linked Systems En Route to Copper Enzyme Models

Third‐Generation Scorpionates [RBpz3]– – How Influential Is the Nondonor Substituent R?

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Mn(CO)₂ Complexes of Cyclopentadienyl/Scorpionate Hybrid Ligands

Reactivity of [(C₅Me₅)Fe(C₅H₄BBr₂)] and [(OC)₃Mn(C₅H₄BBr₂)] toward Et₃SiH: Facile Access to [(OC)₃Mn(C₅H₄BH₂)]₂ and to Boron-Bridged Dinuclear Organometallics

Reactivity of [(C₅Me₅)Fe(C₅H₄BBr₂)] and [(OC)₃Mn(C₅H₄BBr₂)] toward Et₃SiH: Facile Access to [(OC)₃Mn(C₅H₄BH₂)]₂ and to Boron-Bridged Dinuclear Organometallics