Synthesis and X-ray, magnetic and spectroscopic investigations of tetrakis [μ-(β-alanine )-O, O′]bis(diphen ylphosphato)dicopper(II) di(diphenylphosphate) dihydrate

Głowiak, Tadeusz; Podgórska, Irena; Baranowski, J.

doi:10.1016/s0020-1693(00)87691-4

Cited by 10 publications

(13 citation statements)

References 22 publications

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“…A dinuclear complex with a terminally coordinated phosphate ligand is rare (Table 6), structurally characterized examples being [Fe 2 Cl 2 (η 1 -DPP)(TBPO)(MeOH)] 2+ (HTBPO ) N,N,N′,N′-tetrakis(2-benzimidazolylmethyl)-2-hydroxy-1,3diaminopropane) 27 and [Cu 2 (β-ala) 4 (η 1 -DPP) 2 ](DPP) 2 (β-ala ) -OOC(CH 2 ) 2 NH 3 + ). 28 Some additional dinuclear transition metal complexes of phosphate esters are listed in Table 6. [24][25][26][27][28][29][30][31][32][33] The Zn‚‚‚Co interatomic distance is 3.846(1) Å, which is longer by Scheme 2 a a L ) CH3OH.…”

Section: Resultsmentioning

confidence: 99%

“…28 Some additional dinuclear transition metal complexes of phosphate esters are listed in Table 6. [24][25][26][27][28][29][30][31][32][33] The Zn‚‚‚Co interatomic distance is 3.846(1) Å, which is longer by Scheme 2 a a L ) CH3OH. The zinc atom is in a tetrahedral environment surrounded by the two carboxylate oxygen atoms of XDK, the oxygen atom of the bridging DPP, and that of the monodentate DPP.…”

Section: Resultsmentioning

confidence: 99%

“…28 Some additional dinuclear transition metal complexes of phosphate esters are listed in Table 6. [24][25][26][27][28][29][30][31][32][33] The Zn‚‚‚Co interatomic distance is 3.846(1) Å, which is longer by Scheme 2 a a L ) CH3OH. 0.406 Å than that found in the acac-bridged ZnCo complex 2 and by 0.151 Å than that of [Zn II Fe III (BPMP)(µ-η 2 -DPP) 2 ]-(ClO 4 ) 2 (3.695(1) Å).…”

Section: Reaction Of [Znm(xdk)(acac) 2 (Ch 3 Oh) 2 ]‚H 2 O (M ) Co 2+mentioning

confidence: 99%

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Zinc-Containing Carboxylate-Bridged Heterodimetallic Complexes and Their Reactions with Phosphodiester Ligands

1996

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A series of zinc-containing heterodimetallic complexes were prepared by using the dinucleating ligand XDK [H 2 XDK ) m-xylylenediamine bis(Kemp's triacid imide)]. Mononuclear [Zn(XDK)(H 2 O)] (1) reacts with 1 equiv of M(acac) 2 ‚2H 2 O (acac ) 2,4-pentanedionate) to afford the heterodimetallic compounds [Zn II M II (XDK)(acac) 2 (CH 3 OH) 2 ]‚H 2 O (2‚H 2 O, M ) Co, 65% isolated yield; 3‚H 2 O, M ) Mn, 54%; 4‚H 2 O, M ) Fe, 30%; 5‚H 2 O, M ) Ni, 32%). As determined by X-ray crystallography, 2-5 each contain a Zn II M II dinuclear core bridged by XDK and acac ligands. The zinc and M atoms have trigonal bipyramidal and octahedral geometries, respectively. The Zn‚‚‚M separations depend on the metal ion in the octahedral site (2, M ) Co, 3.440(2) Å; 3, M ) Mn, 3.517(1) Å; 4, M ) Fe, 3.492(1) Å; 5, M ) Ni, 3.397(1) Å), a variation which is correlated with the ionic radius of the high-spin octahedral metal ion. The reaction of 2 with diphenyl hydrogen phosphate afforded the bis(phosphate) complex [ZnCo(XDK){µ-η 2 -(PhO) 2 PO 2 }{η 1 -(PhO) 2 PO 2 }(CH 3 OH) 2 (H 2 O)] (7, 49% yield). The ZnCo center is bridged by the XDK through its two carboxylate groups and by a diphenyl phosphate ligand. The other diphenyl phosphate is terminally coordinated to the zinc atom in a monodentate fashion. The Zn‚‚‚Co interatomic distance is 3.846 (1) Å. An analogous bis(phosphate) homodinuclear complex, [Zn 2 (XDK){µ-η 2 -(PhO) 2 PO 2 }{η 1 -(PhO) 2 PO 2 }(CH 3 OH) 2 (H 2 O)] (8), was prepared by reacting [Zn 2 (XDK)(acac) 2 (CH 3 OH) 2 ] (6) with diphenyl hydrogen phosphate in 64% yield. Compound 8, which is isomorphous with 7, has an asymmetrical dizinc core bridged by XDK and a phosphate ligand (Zn‚‚‚Zn ) 3.869(2) Å). The monodentate diphenyl phosphate ligand dissociates from the dimetallic center of 8 in solution, as revealed by molar conductivity and 1 H and 31 P{ 1 H} NMR spectroscopic studies. The resulting free phosphate ligand exchanges with the bridging one in methanol-d 4 . The present results provide a useful synthetic route to carboxylate-bridged heterodimetallic compounds, which are potential models for the active centers in nonredox metalloproteins. Crystal data are as follows. 2: monoclinic, P2 1 /c, a ) 17.725 (7) Å, b ) 12.354(4) Å, c ) 21.815(6) Å, ) 90.45(3)°, V ) 4777(2) Å 3 , Z ) 4; R ) 0.049 and R w ) 0.051 for 3884 reflections with I > 3σ(I). 3: monoclinic, P2 1 /c, a ) 17.292(2) Å, b ) 12.450(1) Å, c ) 21.717(2) Å, ) 91.464(7)°, V ) 4673.9(7) Å 3 , Z ) 4; R ) 0.046 and R w ) 0.051 for 3876 reflections. 4: monoclinic, P2 1 /c, a ) 17.630(1) Å, b ) 12.374(2) Å, c ) 21.771(2) Å, ) 90.306(8)°, V ) 4749.4(7) Å 3 , Z ) 4; R ) 0.041 and R w ) 0.049 for 3248 reflections. 5: monoclinic, P2 1 /c, a ) 17.817(2) Å, b ) 12.241(3) Å, c ) 21.786(2) Å, ) 91.043(9)°, V ) 4751(1) Å 3 , Z ) 4; R ) 0.050 and R w ) 0.058 for 4497 reflections. 7‚CH 3 OH: monoclinic, P2 1 /n, a ) 18.812(2) Å, b ) 16.156(2) Å, c ) 21.760(2) Å, ) 112.836(9)°, V ) 6095(1) Å 3 , Z ) 4; R ) 0.055 and R w ) 0.064 for 5843 reflections. 8‚CH 3 OH: monoclinic,...

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…28 Some additional dinuclear transition metal complexes of phosphate esters are listed in Table 6. [24][25][26][27][28][29][30][31][32][33] The Zn‚‚‚Co interatomic distance is 3.846(1) Å, which is longer by Scheme 2 a a L ) CH3OH. 0.406 Å than that found in the acac-bridged ZnCo complex 2 and by 0.151 Å than that of [Zn II Fe III (BPMP)(µ-η 2 -DPP) 2 ]-(ClO 4 ) 2 (3.695(1) Å).…”

Section: Reaction Of [Znm(xdk)(acac) 2 (Ch 3 Oh) 2 ]‚H 2 O (M ) Co 2+mentioning

confidence: 99%

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Zinc-Containing Carboxylate-Bridged Heterodimetallic Complexes and Their Reactions with Phosphodiester Ligands

1996

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“…The P2−O23 and P2−O24 bond lengths are 1.583(5) and 1.598(5) Å, respectively. There are relatively few dimetallic complexes containing a terminally coordinated phosphate ligand. ,,− …”

Section: Resultsmentioning

confidence: 99%

“…There are relatively few dimetallic complexes containing a terminally coordinated phosphate ligand. 22,24,[45][46][47] Synthesis and Characterization of [Mg(HXDK) 2 (H 2 O) 2 ], 4. Addition of one equiv of bis(4-nitrophenyl) hydrogen phosphate (HBNPP) to a methanolic solution of 1 gave [Mg-(HXDK) 2 (H 2 O) 2 ] (4), the IR spectrum of which indicated the presence of XDK and hydroxyl groups.…”

Section: Synthesis and Characterization Of [Mg 2 (Xdk)(ch 3 Oh) 4 -(H...mentioning

confidence: 99%

Carboxylate- and Phosphate Ester-Bridged Dimagnesium(II), Dizinc(II), and Dicalcium(II) Complexes. Models for Intermediates in Biological Phosphate Ester Hydrolysis

1996

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Carboxylate-bridged dimagnesium(II) complexes were synthesized and characterized by employing the dinucleating ligand XDK, where H 2 XDK is m-xylylenediamine bis(Kemp's triacid imide). The reaction of 1 or 2 equiv of sodium diphenyl phosphate with [Mg 2 (XDK)(CH 3 OH) 4 (H 2 O) 2 (NO 3 )](NO 3 ), 1(NO 3 ), afforded [Mg 2 (XDK){µ-η 2 -(PhO) 2 PO 2 }(CH 3 OH) 3 (H 2 O)(NO 3 )]‚3CH 3 OH (2‚3CH 3 OH) and [Mg 2 (XDK){µ-η 2 -(PhO) 2 PO 2 }{η 1 -(PhO) 2 PO 2 }(CH 3 -OH) 3 (H 2 O)]‚CH 3 OH (3‚CH 3 OH), respectively. These are the first structurally characterized phosphate esterbridged dimagnesium(II) complexes. The reaction of 1 with 1 equiv of bis(4-nitrophenyl) hydrogen phosphate resulted in protonation of one of the carboxylate ligands and liberation of one magnesium(II) ion to give [Mg-(HXDK) 2 (H 2 O) 2 ] (4), an octahedral complex containing two short, low barrier intramolecular OH‚‚‚O hydrogen bonds. The phosphate ester exchange rate of free and bound diphenyl phosphate in 3 in methanol solution was measured by variable-temperature 31 P{ 1 H} NMR spectroscopy and compared to that of structurally analogous dizinc(II), [Zn 2 (XDK){µ-η 2 -(PhO) 2 PO 2 }{η 1 -(PhO) 2 PO 2 }(CH 3 OH) 2 (H 2 O)] (5), and dicalcium(II), [Ca 2 (XDK){µ-η 2 -(PhO) 2 PO 2 }{η 1 -(PhO) 2 PO 2 }(CH 3 OH) 3 (H 2 O)]‚CH 3 OH, (6‚CH 3 OH), complexes. The synthesis and structural characterization of 6 is presented, along with a discussion of the differences between the carboxylate-and phosphate ester-bridged dimagnesium(II), dizinc(II), and dicalcium(II) centers. Crystallographic data are as follows. 1(NO 3 ): monoclinic, P2 1 /c, a ) 11.240(3) Å, b ) 13.019(2) Å, c ) 30.208(7) Å, ) 99.11(1)°, V ) 4365(2) Å 3 , Z ) 4, R ) 0.045, and R w ) 0.054 for 5021 independent reflections with I > 3σ(I). 2‚3CH 3 OH: monoclinic, P2 1 /c, a ) 16.611(5) Å, b ) 16.059(6) Å, c ) 21.930(9) Å, ) 93.34(6)°, V ) 5840(4) Å 3 , Z ) 4, R ) 0.069, and R w ) 0.085 for 3759 independent reflections with I > 2σ(I). 3 . CH 3 OH: monoclinic, P2 1 /n, a ) 18.912(4) Å, b ) 16.254(2) Å, c ) 21.646(5) Å, ) 112.26(2)°, V ) 6158(2) Å 3 , Z ) 4, R ) 0.060, and R w ) 0.072 for 5184 independent reflections with I > 3σ(I). 4: monoclinic, P2 1 /n, a ) 15.210(5) Å, b ) 15.772(3) Å, c ) 13.093(3) Å, ) 96.35(3)°, V ) 3122(1) Å 3 , Z ) 2, R ) 0.069, and R w ) 0.070 for 1840 independent reflections with I > 2σ(I). 6 . CH 3 OH: monoclinic, P2 1 /n, a ) 16.5471(3) Å, b ) 24.3415(6) Å, c ) 16.5865(3) Å, ) 104.2530(10)°, V ) 6475.

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ChemInform Abstract: Synthesis and X‐Ray, Magnetic and Spectroscopic Investigations of Tetrakis[μ‐(β‐alanine)‐O,O′] Tetrakislu‐(β‐alanine)‐0,0′|bis(diphenylphosphato)dicopper(II) Di(diphenylphosphate) Dihydrate.

Głowiak¹,

Podgórska²,

Baranowski³

1986

Chemischer Informationsdienst

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Synthesis and X-ray, magnetic and spectroscopic investigations of tetrakis [μ-(β-alanine )-O, O′]bis(diphen ylphosphato)dicopper(II) di(diphenylphosphate) dihydrate

Cited by 10 publications

References 22 publications

Zinc-Containing Carboxylate-Bridged Heterodimetallic Complexes and Their Reactions with Phosphodiester Ligands

Zinc-Containing Carboxylate-Bridged Heterodimetallic Complexes and Their Reactions with Phosphodiester Ligands

Carboxylate- and Phosphate Ester-Bridged Dimagnesium(II), Dizinc(II), and Dicalcium(II) Complexes. Models for Intermediates in Biological Phosphate Ester Hydrolysis

ChemInform Abstract: Synthesis and X‐Ray, Magnetic and Spectroscopic Investigations of Tetrakis[μ‐(β‐alanine)‐O,O′] Tetrakislu‐(β‐alanine)‐0,0′|bis(diphenylphosphato)dicopper(II) Di(diphenylphosphate) Dihydrate.

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