Synthesis of an anionic tridentate phosphinoborate and its reaction chemistry with Sn(II)

Barney, Alfred A.; Heyduk, Alan F.; Nocera, Daniel G.

doi:10.1039/a906560a

Cited by 68 publications

(37 citation statements)

References 19 publications

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“…The discorpionate [10] 2À is designed to mimic the two ligation sites of the copper enzymes peptidylglycine a-hydroxylating monooxygenase and dopamine bmonooxygenase in which the cooperative action of one [his 3 Cu] and one [his 2 A C H T U N G T R E N N U N G (met)Cu] fragment leads to oxidative CÀH activation (his = histidine; met = methionine). In a systematic study, we first investigated the coordination properties of the monotopic tripod [5] À toward Cu I and Cu II ions and isolated 2:1 complexes KA C H T U N G T R E N N U N G [Cu I (5) 2 ] (K [11]) and [Cu II (5) 2 ] (12).…”

Section: Quantum Chemical Calculationsmentioning

confidence: 99%

“…One way to alter the donor/acceptor properties of scorpionate ligands over a wider range is to replace the pyrazolyl rings by phosphorus-(B [3][4][5] ) or sulfur-containing groups (C, [6,7] D; [8][9][10][11][12] Figure 1). Similar to the parent scorpionates A, ligands B-D provide a monoanionic, tridentate, face-capping coordination mode, but they differ from A with regard to the softness of their donor sets.…”

Section: Introductionmentioning

confidence: 99%

“…Very recently, even hybrid scorpionates of A-D have become available, which provide nitrogen and phosphorus Abstract: TMEDA-free (TMEDA: tetramethylethylenediamine) LiCH 2 -A C H T U N G T R E N N U N G SMe is a suitable reagent for the selective introduction of (methylthio)methyl groups into PhBBr 2 and its p-silylated derivative Me 3 ( [10] 2À ) that mimics the two ligation sites of the copper enzymes peptidylglycine a-hydroxylating monooxygenase and dopamine b-monooxygenase. Treatment of the monotopic tripod [5] À with CuCl and CuBr 2 results in the formation of complexes K[Cu (5) ((N 2 P), [13,14] (NP 2 ) [15] ) or nitrogen and sulfur donors ((N 2 S), [16] (NS 2 ) [17][18][19][20][21][22] ).…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Quantum Chemical Calculationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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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“…The anionic tris(phosphino)borates [PhB(CH 2 PR 2 ) 3 ] À , originally reported in 1999 almost simultaneously by the research groups of Tilley [36] and Nocera [116], are excellent σ-donor ligands and weak π-acceptors that, like the tris(carbene)borates described above, are well poised to stabilize transition metals in unusually high oxidation states. Thus, a number of noteworthy complexes of iron that can be regarded as putative intermediates in the process of nitrogen fixation have been synthesized and studied by a variety of spectroscopic, structural, and computational methods [117].…”

Section: Tris(phosphino)boratesmentioning

confidence: 97%

“…3). In addition, related ligands based on carbene [34,35], phosphine [36,37], thioether [38], thione [39][40][41], and selone [39] donor moieties have been studied during the past 20 years or so and will be discussed in more detail below (Fig. 4).…”

Section: Scorpionate Ligandsmentioning

confidence: 99%

Synthetic Bioinorganic Chemistry: Scorpionates Turn 50

Rabinovich

2016

Structure and Bonding

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The coordination chemistry of scorpionates, anionic tripodal boroncentered ligands that readily bind to virtually all main group, transition, and f-block metals, has had a profound effect in the development of synthetic bioinorganic chemistry during the past 50 years. Highlighted in this article are some of the most meaningful results published in the area, primarily in the preparation of structural and functional model compounds for the active sites in metalloproteins and metalloenzymes, a theme that encompasses topics as diverse as nitrogen fixation and heavy metal poisoning. It has also been 50 years since the genesis of Structure and Bonding, so let this account also be a celebration of the many contributions that the staunch serial has had on the entire field of inorganic chemistry during the past half century.

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[Diphenylphosphino]methyllithium

Choukroun¹,

Lorber²

2004

Encyclopedia of Reagents for Organic Synthesis

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Synthesis of an anionic tridentate phosphinoborate and its reaction chemistry with Sn(II)

Cited by 68 publications

References 19 publications

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

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

Synthetic Bioinorganic Chemistry: Scorpionates Turn 50

[Diphenylphosphino]methyllithium

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