Hydrolytic Cleavage of Diphosphates, Sulfonatophosphates, and Disulfonates by (Pyrazolylborate)zinc Hydroxide Complexes

Weis, K. H.; Vahrenkamp, Heinrich

doi:10.1002/(sici)1099-0682(199802)1998:2<271::aid-ejic271>3.0.co;2-x

Cited by 28 publications

(35 citation statements)

References 25 publications

(10 reference statements)

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“…Both provide one point of attachment per phosphate unit, thereby activating the PϪO function, and leave coordination sites at the zinc or space in the coordination sphere for the hydrolytic nucleophile. We favor the monodentate attachment, as we have already presented preparative [15,16] and mechanistic [9,10] evidence in support of it. This paper has proved its existence in the environment of encapsulating ligands, which resembles most closely that in enzymes.…”

Section: Discussionmentioning

confidence: 99%

“…[15] Experimental Section General: For general working and measuring procedures, see ref. [19] The lithium and sodium salts and the free acids of the triorgano- [20,21] and diorganodiphosphates, [2,20,22] as well as the TBP [11] coligands and Tp*ZnϪOH, [23] were stored under inert conditions.…”

Section: Discussionmentioning

confidence: 99%

“…Accordingly, the ZnϪO bond is almost as short as in tetrahedral zincϪphosphate complexes. [15,16] The diphosphates are coordinated to zinc in a clearly monodentate fashion. Although one PϪO donor function on the second phosphorus atom is oriented towards the zinc ion, its ZnϪO distance (3.5Ϫ4.1 Å ) is outside the range for bonding.…”

Section: (Tba)zn Complexes Of Diorganodiphosphatesmentioning

confidence: 99%

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Diphosphate−Zinc Complexes with Encapsulating Tripodal Coligands

Müller-Hartmann

Vahrenkamp

2000

Eur. J. Inorg. Chem.

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Tris(benzimidazolylmethyl)amine (TBA) and tris(pyrazolyl)borate (Tp) ligands have been used to prepare ternary zinc complexes with triorganodiphosphates (R3POP−), triorgano‐methylenediphosphonates (R3PCP−), and diorganodiphosphates (R2POP2−). The complex types [(TBA)Zn(R3POP)]+ and [(TBA)Zn(R3PCP)]+ have been assigned as containing trigonal‐bipyramidal zinc with monodentate diphosphate ligands. By X‐ray structure determination, the complex type [(TBA)Zn(R2POP)] has been found to contain the same ZnN4O coordination pattern, which has also been assigned to the dinuclear complexes [(TBA)Zn(R2POP)Zn(TBA)]2+ incorporating the diphosphates as bis‐monodentate bridging ligands. The same monodentate and bis‐monodentate attachment of the diphosphates, but with tetrahedral zinc in a ZnN3O environment, has been identified in the pyrazolylborate complexes TpZn(R3POP) and TpZn(R2POP)ZnTp.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: (Tba)zn Complexes Of Diorganodiphosphatesmentioning

confidence: 99%

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Diphosphate−Zinc Complexes with Encapsulating Tripodal Coligands

Müller-Hartmann

Vahrenkamp

2000

Eur. J. Inorg. Chem.

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“…[22] Our mechanistic implications for these and similar hydrolytic reactions with ZnϪOH species [23,24] require that the substrate (e.g. the pyrophosphate) is attached to only one zinc ion through only one oxygen donor during the activation step, which is in contrast to common schemes for phosphate hydrolyses [3,8] that imply attachment of zinc to two PϪO units or the attachment of two metal ions to one phosphate entity.…”

Section: Introductionmentioning

confidence: 99%

Diphosphate−Zinc Complexes with Chelating Coligands

Müller-Hartmann

Vahrenkamp

2000

Eur. J. Inorg. Chem.

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Zinc perchlorate, diorganodiphosphates (POP2−), and chelating ligands L (L = 1,10‐phenanthroline, neocuproine, 2,2′‐bipyridine, oxinate) yield three types of ternary complexes. Type 1 (L2Zn·POP) contains octahedral zinc bound by the diphosphate as an OPOPO chelate ligand. Type 2 (LZn·POP) consists of dimeric complexes containing five‐coordinate zinc, with the diphosphates acting as OPOPO chelate ligands for one zinc ion and as OPO bridges between two zinc ions. Type 3 (L2Zn2·POP), observed only for oxinate, is proposed to contain two five‐coordinate zinc ions bridged by the diphosphate as a tetradentate ligand.

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“…Mononuclear, [1][2] binuclear, [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] trinuclear, 17,18 tetranuclear [19][20][21][22][23] and polymeric 24 complexes have been reported in which the phosphate moieties adopt monodentate, chelating, and bridging binding modes. These examples include heterometallic complexes.…”

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Synthesis, Characterization, and Crystal Structures of Novel Coordination Polymers of Praseodymium(III) and Neodymium(III) Containing Dialkyl Phosphate

Rafizadeh¹,

Amani²,

Mortazavi³

2009

Bulletin of the Korean Chemical Society

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Metal complexes incorporating various types of phosphate moieties are being examined in order to explore the metalbinding properties of such ligands and to elucidate the importance of these interactions in biological systems. Mononuclear, 37 In this complex, DMP is not bonded to the metal, and acts as a independent counter-ion. We have also reported the synthesis and crystal structures of [Fe 16 38 within which an macromolecule constellation consisting of sixteen iron ion connected by twelve bridging dimethyl phosphate, twelve bridging acetate, eight µ3-oxo, four µ3-OH, four µ-OH and four dimethyl sulfoxide ligands. We now report on the synthesis, characterization and crystal structure of novel polymer of praseodymium(III) and neodymium(III) complexes. Experimental SectionAll chemicals were purchased from Merck and Aldrich. Infrared spectra (4000-250 cm -1 ) of solid samples were taken as 1% dispersion in KBr pellets using a Shimadzu-470 spectrometer. H NMR, 13C NMR and 31 P NMR spectra were acquired on a Bruker AC-300 MHz spectrometer at ambient temperature in D2O. Melting points were is uncorrected and were obtained by a Kofler Heizbank Rechart type 7841 melting point apparatus.Synthesis of [Nd(µ-DEP)3]n (1). Triethyl phosphate (3.31g, 3.1 mL, 18 mmol) was added to a solution of NdCl 3 (0.93 g, 3.6 mmol) in ethanol (40 mL) and DMSO (5mL) and the resulting pale violet solution was stirred at 40 °C for 30 minute. Then, it was left to evaporate slowly at room temperature. After two months, colorless prismatic crystals of 1 were isolated (yield 1.62 g, 74.56%, m.p < 300 o C). IR (KBr, ): 2984s, 2940m, 2912m (νCH), 1446w, 1399m, 1372w, 1197s, 1181s, 1168s, 1117s, 1093s, 1066s, 1044s (νC-O-P), 977s, 825s, 778m (νP-O), 576m, 541m, 504m, 409w, 388m, 332w (νNd-O

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Hydrolytic Cleavage of Diphosphates, Sulfonatophosphates, and Disulfonates by (Pyrazolylborate)zinc Hydroxide Complexes

Cited by 28 publications

References 25 publications

Diphosphate−Zinc Complexes with Encapsulating Tripodal Coligands

Diphosphate−Zinc Complexes with Encapsulating Tripodal Coligands

Diphosphate−Zinc Complexes with Chelating Coligands

Synthesis, Characterization, and Crystal Structures of Novel Coordination Polymers of Praseodymium(III) and Neodymium(III) Containing Dialkyl Phosphate

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