Bidentate bonding mode of tetrahydroborate and nitrite towards copper(II) in open-faced macrocyclic complexes

Aqra, Fathi

doi:10.1007/s11243-004-3223-8

Cited by 1 publication

(3 citation statements)

References 35 publications

(33 reference statements)

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“…This is, therefore, consistent with the IR spectroscopic data. The BH 2 Cu mode can either be considered as two separate B-H agostic type interactions (η 2 ,η 2 ) or as a three-centered dihydroborate interaction [1][2][3][4]. This coordination mode in the mono-substituted ligand allows for a different morphology about the copper center in comparison to that found in complex 3 [36].…”

Section: Structural Characterization Of Copper Complexesmentioning

confidence: 99%

“…The numbering scheme used for NMR assignments is highlighted in Figure 5. (6)), 132.9 (d, 1 J CP = 32 Hz, P ipso (C 6 H 5 ) 3 ), 133.8 (d, 3 J CP = 16 Hz, P meta (C 6 H 5 ) 3 ), 135.0 ( mp CH-(5)), 146.5 ( mp CH-(3)), 175.9 ( mp C=S-(2)). 31…”

Section: General Remarksmentioning

confidence: 99%

“…The coordination chemistry of borohydride and substituted borohydride units with transition metals has been a major focus of research over many decades now [1][2][3][4][5][6][7][8][9]. One particular focus of research has been on substituted borohydride units attached to other donor functional groups.…”

Section: Introductionmentioning

confidence: 99%

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Adding to the Family of Copper Complexes Featuring Borohydride Ligands Based on 2-Mercaptopyridyl Units

et al. 2019

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Borohydride ligands featuring multiple pendant donor functionalities have been prevalent in the chemical literature for many decades now. More recent times has seen their development into new families of so-called soft scorpionates, for example, those featuring sulfur based donors. Despite all of these developments, those ligands containing just one pendant group are rare. This article explores one ligand family based on the 2-mercaptopyridine heterocycle. The coordination chemistry of the monosubstituted ligand, [H 3 B(mp)] − (mp = 2-mercaptopyridyl), has been explored. Reaction of Na[BH 3 (mp)] with one equivalent of Cu (I) Cl in the presence of either triphenylphosphine or tricyclohexylphosphine co-ligands leads to the formation of [Cu{H 3 B(mp)}(PR 3 )] (R = Ph, 1; Cy, 2), respectively. Structural characterization confirms a κ 3 -S,H,H coordination mode for the borohydride-based ligand within 1 and 2, involving a dihydroborate bridging interaction (BH 2 Cu) with the copper centers.Inorganics 2019, 7, 93 2 of 11 differences when compared to Trofimenko's original scorpionates. The ligand was based on soft sulfur donor atoms [16], and perhaps more significantly, greater flexibility had been incorporated into the ligand by addition of the extra atom between the boron and the donor atom. It was this greater flexibility within the ligand structure that opened up the potential for activation at the boron bridgehead and formation of metal-borane (metallaboratrane) complexes [17][18][19][20][24][25][26][27], giving rise to reactivity not observed in the analogous polypyrazolylborate ligands [10][11][12][13][14][15][16].Inorganics 2019, 7, x FOR PEER REVIEW 2 of 11 differences when compared to Trofimenko's original scorpionates. The ligand was based on soft sulfur donor atoms [16], and perhaps more significantly, greater flexibility had been incorporated into the ligand by addition of the extra atom between the boron and the donor atom. It was this greater flexibility within the ligand structure that opened up the potential for activation at the boron bridgehead and formation of metal-borane (metallaboratrane) complexes [17][18][19][20][24][25][26][27], giving rise to reactivity not observed in the analogous polypyrazolylborate ligands [10][11][12][13][14][15][16].

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