New unexpected coordination modes of azide and picolinato anions acting as bridging ligands between copper(II) and sodium or potassium ions. Synthesis, crystal structures and spectral characterizations of [MCu(picolinato)(N3)2]n (M = Na or K) complexes

CuII Complexes and Coordination Polymers with Pyridine or Pyrazine Amides and Amino Benzamides—Structures and EPR Patterns

“…O amide occurs in this plane only in chelates with these N functions, NH 2amide -Cu binding was not observed. The Cu II -ligand bonds in the equatorial plane lie in the range of 1.93 to 2.08 Å and are comparable with previously reported complexes of these ligands [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][38][39][40][41][42][43][44][45][46]. Remarkably, the shortest Cu-ligand bonds were of the Cu-O amide type and were found for the chelating Pia, Pya, and 2-Aba ligands, but also for terminating binding of the 4-Aba ligands including the 4-HAba For the labelling of the structures as OE in Table 2, two axial ligands must be present in a distance elongated to about 10-20% compared to the same ligand in an equatorial position [42].…”

CuII Complexes and Coordination Polymers with Pyridine or Pyrazine Amides and Amino Benzamides—Structures and EPR Patterns

“…O amide occurs in this plane only in chelates with these N functions, NH 2amide -Cu binding was not observed. The Cu II -ligand bonds in the equatorial plane lie in the range of 1.93 to 2.08 Å and are comparable with previously reported complexes of these ligands [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][38][39][40][41][42][43][44][45][46]. Remarkably, the shortest Cu-ligand bonds were of the Cu-O amide type and were found for the chelating Pia, Pya, and 2-Aba ligands, but also for terminating binding of the 4-Aba ligands including the 4-HAba For the labelling of the structures as OE in Table 2, two axial ligands must be present in a distance elongated to about 10-20% compared to the same ligand in an equatorial position [42].…”

A -1,1,1,3,3,3 Azide Anion inside a Trigonal Prism of Silver Centers

“…In the course of our studies, we sought to synthesize a number of cycloplatinated species that would show novel mesogenic behavior. [6] It is also similar to the length of 1.973 (11) for the cationic Pt IV ± carbene complex [PtCl 2 {C(NHMe)(NHC 6 H 4 Cl)}(PEt 3 ) 2 ]ClO 4 , [7] and significantly shorter than that in the non-carbene cycloplatinated species [{PtCl(tBu 2 PCMe 2 CH 2 )} 2 ] (2.062(6) ) [8] or Pt II ± C aryl single bond lengths of 1.98 ± 2.02 in arylplatinum complexes. [5] When we used pyridine 1 we isolated the expected cycloplatinated product 2, formed by coordination of the pyridine followed by intramolecular CÀH activation, in high yield.…”

“…The PtÀC bond length of 1.951 (9) is very similar to the values observed for the Pt 0 ± carbene complex derived from 1,3-dimesitylimidazol-2-ylidene (1.959 (8) and 1.942 (8) ). [6] It is also similar to the length of 1.973 (11) for the cationic Pt IV ± carbene complex [PtCl 2 {C(NHMe)(NHC 6 H 4 Cl)}(PEt 3 ) 2 ]ClO 4 , [7] and significantly shorter than that in the non-carbene cycloplatinated species [{PtCl(tBu 2 PCMe 2 CH 2 )} 2 ] (2.062(6) ) [8] or Pt II ± C aryl single bond lengths of 1.98 ± 2.02 in arylplatinum complexes. [9,10] Two shorter PtÀC bonds have been reported: a bond length of 1.82 (6) for the platinum ± carbene complex [{PtCl(tBuCH 2 COiPr)} 2 ] [11] (though given the relatively large estimated standard deviations associated with this measurement, this value is not significantly different from ours), and a…”

Differential Reactivity between Two Copper Sites in Peptidylglycine α-Hydroxylating Monooxygenase

“…This Cu 2+ -:(N 3 − )-Na + motif has not been previously observed in proteins and is very rare even in synthetic metal complexes 37. In addition, the loop Asp 127 -Glu 128 -Gly 129 -Thr 130 moves closer to the Cu M site, in comparison to the free enzyme (Figure 4).…”

“…Electron density maps also showed a sodium ion bound to the azide ligand, behaving as a μ(1,1)-bridging bidentate ligand connecting the Cu M 2+ to the Na + (Figure ). This Cu 2+ −(N 3 − )−Na + motif has not been previously observed in proteins and is very rare, even in synthetic metal complexes . In addition, the loop Asp 127 −Glu 128 −Gly 129 −Thr 130 moves closer to the Cu M site, in comparison to its position in the free enzyme (Figure ).…”

CuII Complexes and Coordination Polymers with Pyridine or Pyrazine Amides and Amino Benzamides—Structures and EPR Patterns

“…O amide occurs in this plane only in chelates with these N functions, NH 2amide -Cu binding was not observed. The Cu II -ligand bonds in the equatorial plane lie in the range of 1.93 to 2.08 Å and are comparable with previously reported complexes of these ligands [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][38][39][40][41][42][43][44][45][46]. Remarkably, the shortest Cu-ligand bonds were of the Cu-O amide type and were found for the chelating Pia, Pya, and 2-Aba ligands, but also for terminating binding of the 4-Aba ligands including the 4-HAba For the labelling of the structures as OE in Table 2, two axial ligands must be present in a distance elongated to about 10-20% compared to the same ligand in an equatorial position [42].…”

A -1,1,1,3,3,3 Azide Anion inside a Trigonal Prism of Silver Centers

“…In the course of our studies, we sought to synthesize a number of cycloplatinated species that would show novel mesogenic behavior. [6] It is also similar to the length of 1.973 (11) for the cationic Pt IV ± carbene complex [PtCl 2 {C(NHMe)(NHC 6 H 4 Cl)}(PEt 3 ) 2 ]ClO 4 , [7] and significantly shorter than that in the non-carbene cycloplatinated species [{PtCl(tBu 2 PCMe 2 CH 2 )} 2 ] (2.062(6) ) [8] or Pt II ± C aryl single bond lengths of 1.98 ± 2.02 in arylplatinum complexes. [5] When we used pyridine 1 we isolated the expected cycloplatinated product 2, formed by coordination of the pyridine followed by intramolecular CÀH activation, in high yield.…”

“…The PtÀC bond length of 1.951 (9) is very similar to the values observed for the Pt 0 ± carbene complex derived from 1,3-dimesitylimidazol-2-ylidene (1.959 (8) and 1.942 (8) ). [6] It is also similar to the length of 1.973 (11) for the cationic Pt IV ± carbene complex [PtCl 2 {C(NHMe)(NHC 6 H 4 Cl)}(PEt 3 ) 2 ]ClO 4 , [7] and significantly shorter than that in the non-carbene cycloplatinated species [{PtCl(tBu 2 PCMe 2 CH 2 )} 2 ] (2.062(6) ) [8] or Pt II ± C aryl single bond lengths of 1.98 ± 2.02 in arylplatinum complexes. [9,10] Two shorter PtÀC bonds have been reported: a bond length of 1.82 (6) for the platinum ± carbene complex [{PtCl(tBuCH 2 COiPr)} 2 ] [11] (though given the relatively large estimated standard deviations associated with this measurement, this value is not significantly different from ours), and a…”

Differential Reactivity between Two Copper Sites in Peptidylglycine α-Hydroxylating Monooxygenase

“…This Cu 2+ -:(N 3 − )-Na + motif has not been previously observed in proteins and is very rare even in synthetic metal complexes 37. In addition, the loop Asp 127 -Glu 128 -Gly 129 -Thr 130 moves closer to the Cu M site, in comparison to the free enzyme (Figure 4).…”

“…Electron density maps also showed a sodium ion bound to the azide ligand, behaving as a μ(1,1)-bridging bidentate ligand connecting the Cu M 2+ to the Na + (Figure ). This Cu 2+ −(N 3 − )−Na + motif has not been previously observed in proteins and is very rare, even in synthetic metal complexes . In addition, the loop Asp 127 −Glu 128 −Gly 129 −Thr 130 moves closer to the Cu M site, in comparison to its position in the free enzyme (Figure ).…”

CuII Complexes and Coordination Polymers with Pyridine or Pyrazine Amides and Amino Benzamides—Structures and EPR Patterns

“…O amide occurs in this plane only in chelates with these N functions, NH 2amide -Cu binding was not observed. The Cu II -ligand bonds in the equatorial plane lie in the range of 1.93 to 2.08 Å and are comparable with previously reported complexes of these ligands [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][38][39][40][41][42][43][44][45][46]. Remarkably, the shortest Cu-ligand bonds were of the Cu-O amide type and were found for the chelating Pia, Pya, and 2-Aba ligands, but also for terminating binding of the 4-Aba ligands including the 4-HAba For the labelling of the structures as OE in Table 2, two axial ligands must be present in a distance elongated to about 10-20% compared to the same ligand in an equatorial position [42].…”

A -1,1,1,3,3,3 Azide Anion inside a Trigonal Prism of Silver Centers

“…In the course of our studies, we sought to synthesize a number of cycloplatinated species that would show novel mesogenic behavior. [6] It is also similar to the length of 1.973 (11) for the cationic Pt IV ± carbene complex [PtCl 2 {C(NHMe)(NHC 6 H 4 Cl)}(PEt 3 ) 2 ]ClO 4 , [7] and significantly shorter than that in the non-carbene cycloplatinated species [{PtCl(tBu 2 PCMe 2 CH 2 )} 2 ] (2.062(6) ) [8] or Pt II ± C aryl single bond lengths of 1.98 ± 2.02 in arylplatinum complexes. [5] When we used pyridine 1 we isolated the expected cycloplatinated product 2, formed by coordination of the pyridine followed by intramolecular CÀH activation, in high yield.…”

“…The PtÀC bond length of 1.951 (9) is very similar to the values observed for the Pt 0 ± carbene complex derived from 1,3-dimesitylimidazol-2-ylidene (1.959 (8) and 1.942 (8) ). [6] It is also similar to the length of 1.973 (11) for the cationic Pt IV ± carbene complex [PtCl 2 {C(NHMe)(NHC 6 H 4 Cl)}(PEt 3 ) 2 ]ClO 4 , [7] and significantly shorter than that in the non-carbene cycloplatinated species [{PtCl(tBu 2 PCMe 2 CH 2 )} 2 ] (2.062(6) ) [8] or Pt II ± C aryl single bond lengths of 1.98 ± 2.02 in arylplatinum complexes. [9,10] Two shorter PtÀC bonds have been reported: a bond length of 1.82 (6) for the platinum ± carbene complex [{PtCl(tBuCH 2 COiPr)} 2 ] [11] (though given the relatively large estimated standard deviations associated with this measurement, this value is not significantly different from ours), and a…”

Differential Reactivity between Two Copper Sites in Peptidylglycine α-Hydroxylating Monooxygenase

“…This Cu 2+ -:(N 3 − )-Na + motif has not been previously observed in proteins and is very rare even in synthetic metal complexes 37. In addition, the loop Asp 127 -Glu 128 -Gly 129 -Thr 130 moves closer to the Cu M site, in comparison to the free enzyme (Figure 4).…”

“…Electron density maps also showed a sodium ion bound to the azide ligand, behaving as a μ(1,1)-bridging bidentate ligand connecting the Cu M 2+ to the Na + (Figure ). This Cu 2+ −(N 3 − )−Na + motif has not been previously observed in proteins and is very rare, even in synthetic metal complexes . In addition, the loop Asp 127 −Glu 128 −Gly 129 −Thr 130 moves closer to the Cu M site, in comparison to its position in the free enzyme (Figure ).…”