Regional rule for the optical activity of conformational isomers of octahedral transition metal complexes

Bosnich, B.; Harrowfield, J. M.

doi:10.1021/ja00765a028

Cited by 79 publications

(39 citation statements)

References 4 publications

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“…Compound (11) was prepared using the synthetic procedure of Basolo [8] for the preparation of [cis-ctCo(trien)C12]Cl" 3H20, which was known from the work of Bosnich [9] to result in the trans-dichloro chloride derivative of 3,2,3-tet. The chloride of (II) was converted to the nitrate by addition of excess NaNO3 and concentrating the solution in a rotary evaporator.…”

Section: Synthesesmentioning

confidence: 99%

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The phenomenon of conglomerate crystallization. Part 40: The crystallization behavior oftrans- Co(III) amines (+)546-trans-[Co(3,2,3-tet)(NO2)2]Cl·3H2O (I), (−)589 -trans-[Co(3,2,3-tet)Cl2]NO3 (II), and of (+)546-trans-[Co(3,2,3-tet)(NO2)2]NO3 (III)

et al. 1995

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A racemic solution of (I) crystallizes as a conglomerate from which a crystal we selected was found to be (+) 2, . A total of 2305 data were collected over the range of 4 ~ _< 20 _ 55~ of these, 1724 (independent and with I >_ 3a(1)) were used in the structural analysis. Data were corrected for absorption (~t = 11.920 cm-I), and the relative transmission coefficients ranged from 0.8258 to 0.9565. Refinement was carded out for both lattice enantiomorphs, and at this stage the R(F) and R~.(F) residuals were, respectively, 0.0381 and 0.0479 for (+ + +) and 0.0448 and 0.0532 for (---). Thus, the former was selected as correct for our specimen, and the final cycle of refinement with the (++ +) model converged to R(F) and R,.(F) of 0.0315 and 0.0365. A racemic solution of (II) crystallizes as a conglomerate from which a crystal we selected was found to be 2,Cl2]N03 (II), CoCIzO3NsCsH22. It crystallizes in the enantiomorphic space groujp, P21 with lattice constants a = 6.395(2) ,~, b = 8.886(2) ,~., c = 13.185(2) :k, and/3 = 99.24(2)~ V = 739.59 ,~3 and d(calc. M.W. = 366.14, Z = 2) = 1.646 g cm -3. A total of 2912 data were collected over the range of 4 ~ _< 20 _< 64~ of these, 2147 (independent and with I >_ 3a(1)) were used in the structural analysis, Data were corrected for absorption (/z = 15.424 cm-I), and the relative transmission coefficients ranged from 0.9632 to 0.9985. Refinement was carded out for both lattice enantiomorphs, and the final R(F) and R,,.(F) residuals were, respectively, 0.0326 and 0.0328 for (+ + +) and 0.0347 and 0.0348 for (---). Thus, the (+ + +) was selected as correct for our specimen. A racemic solution of (III) crystallizes as a conglomerate from which a crystal we selected was found to be (+) 2, Bernal, Cetrullo, Cai, and Massoud correct for our specimen, and the final cycle of refinement with the (---) model converged to R(F) and Rw(F) of 0.0436 and 0.0421. For all three compounds, the six-membered rings are chairs; the secondary nitrogens are chiral centers, and the five-membered rings are ordered and conformationally dissymmetric, as expected. Coincidentally, in (I), (II), and (III) the central rings are right-handed helices with ~t(+50.0~ ~5(+53.3~ and t5(+48.3~ respectively. Thus, the secondary nitrogens of all three cations are (R), rendering the cations chiral. The incidence of conglomerate crystallization in trans coordination compounds is rare, and those known are asymmetrically substituted (see Ref. 4 for the four known cases). Thus, the incidence of such crystallization mode in a new series of [trans-Co(amine ligands)X2] § cations bearing symmetrical pairs of trans ligands was an unexpected and welcomed event. In all three cases, the counteranions are bonded to the hydrogens of the terminal --NH2 moieties, thus forming an overall entity which resembles a macrocycle. In fact, parallels between the crystallization behavior of our compounds and that of macrocycles bearing related fragments is discussed. Finally, in the three compounds, homochiral cations are linked into infin...

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Section: Synthesesmentioning

confidence: 99%

“…The results are listed in Table IV, which verify the correctness of the assignment of absolute configuration based on the R-factor arguments. All statements made by Payne in his earlier reports [12,13] using preresolved compounds provided by Bosnich [9] 5. A view of the asymmetric unit of (III).…”

Section: Absolute Configurations Of (I) (Ii) and (Iii)mentioning

confidence: 99%

The phenomenon of conglomerate crystallization. Part 40: The crystallization behavior oftrans- Co(III) amines (+)546-trans-[Co(3,2,3-tet)(NO2)2]Cl·3H2O (I), (−)589 -trans-[Co(3,2,3-tet)Cl2]NO3 (II), and of (+)546-trans-[Co(3,2,3-tet)(NO2)2]NO3 (III)

et al. 1995

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“…176.16 ( Co(2)--N(6)--C (11) 108.0(1) C(10)--N(6)--C (11) 110.7(2) Co(2)--N(7)--C(12) 109.4(1) Co(2)--N(7)--C(13) 106.6(1) C(12)--N(7)--C(13) 114.7(2) Co (1) 153.6 Ow (9)…”

Section: Crystallographyunclassified

“…1.942 (2) O (9) (4) 1.515 (3) 1.511 (3) 1.534 (3) 1.5o1 (4) 1.509(3) (5) 113.2(2) Co(1)--N(4)--C (6) 113.1(1) Co(2)--N(5)--C (9) 112.8(2) Co(2)--N(6)--C (10) 107.8(2) Co(2)--N(6) C (11) 108.5(2) C(10)--N(6)--C (11) 116.5(2) Co(2)--N(7)--C (12) 110.1(2) Co(2) N(7)--C (13) 107.4(2) C(12) N(7)--C (13) 113.8(2) Co(2)--N(8)--C (14) 112.9(2) 0 (9) (3) to solve the structure in C2, Cm and C2/m. The only reasonable results were obtained with space group Cm and the excellent refinement results in this space group justifies its selection.…”

Section: Bond Distancesmentioning

confidence: 99%

The phenomenon of conglomerate crystallization. XXXV. The crystallization behaviour of {cis-α-Co(trien)ox]Cl}2·9H2O (1), cis-β-Co(3,2,3-tet)ox]Cl·4H2O(2), {cis-α-Co(trien)ox]NO3}2· H2O (3), and [mer-Co(dien)ox (NO2)] (4)

Bernal

Cetrullo

Cai

1994

Transition Met Chem

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The phenomenon of conglomerate crystallization. XXXV. The crystallization behaviour of { [cis-c -Co(trien)ox]C1}z.9HzO (1), [cis-fi-Co(3,2,3-tet)ox]Cl'4H20 (2), { [cis-c -Co(trien)ox]N03} 2. H20 (3), and [mer-Co(dien)ox (NO2)] (4) SummaryAs expected from previous studies, the four title compounds crystallize as racemates from H20 solutions allowed to evaporate at room temperature (ca. 18 ~ C). All four complexes have been characterized by X-ray crystallography.The outer, six-membered rings in (2) are in the chair conformation; and, in the first three species, the secondary nitrogens are chiral centres. In (1) the five-membered rings of the two cations in the asymmetric unit are characterized: Co(l), 6, 6 and 2, with the chiralities of the secondary nitrogens (S) and (S); Co(2), 2,2 and 6, with secondary nitrogens (R) and (R). In (3), the five-membered rings of the two cations in the asymmetric unit are: Co(l), 6, 6 and 2, with secondary nitrogens (S) and (S); Co(2), 6, )o and 6, with secondary nitrogens (S) and (S). In (2), the five-membered ring is 6 and the chiralities of the secondary nitrogens are (R) and (R). In (4), the unique five-membered ring is 2 and the central --NH--fragment lies at a mirror plane.Comparison of the crystallization pathways of these complexes with those of related substances are made, and suggestions as to why (1) (4) select the racemic crystallization pathway are offered.

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“…According to the socalled perturbation model for the optical activity of transition metal complexes, the CD of the d-d bands arises from dissymmetric interaction between the electrons and nuclei of the dissymmetrically oriented ligand and the d electrons on the metal ion (Bosnich and Harrowfield, 1972;Mason, 1971). For these complexes, there are four dissymmetric sources, arising from puckering of the chelate ring, the methyl group (Mel) of the chelate ring, the distortions of the donor nitrogen atoms, and the alky groups on the nitrogen atom.…”

Section: Molecular Structuresmentioning

confidence: 99%

The crystal and molecular structures of dichloro(N¹ ,Ν¹ -dimethyl-(S)-1,2-propanediamine)- palladium(II) hemihydrate and dichloro(N¹,N¹- diethyl-(S)-1,2-propanediamine) palladium(II)

Ueda¹,

Suzuki²

1980

Zeitschrift Für Kristallographie - Crystalline Materials

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The crystal structures of the title compounds, [PdCl 2 {N 1 -Me 2 -(S)-pn}] · ?H 2 0 and [PdCl 2 {N 1 -Et 2 -(S)-pn}], were determined from three dimensional X-ray diffraction data. The space group of the former is i>2, and the crystal data are a = 7.988(2), b = 9.785(3), c = 20.827(6) A, β = 90.13(2)°, and Ζ = 6. Those of the latter are P2 1 2 1 2 1 , a = 13.726(1), b = 14.945(1), c = 11.405(1)Ä, and Ζ = 8. The intensity data were measured by an automated four-circle diffractometer and the structures were solved by a heavy atom method and by a minimum residual method. The final R factors were 0.029 and 0.031, respectively, for the observed reflexions. In [PdCl^N 1 -Me 2 -(S)-pn}] · ΐ H 2 0, the molecules are held together by the strong hydrogen bonds between the CI and Ν atoms. In [PdC^fN'-Etj-iS^pn}], formation of the hydrogen bonds is hindered to some extent by the ethyl groups. All the diamine chelate rinp adopt δ conformation. The deviations of the atoms from the molecular planes are considerably affected by the crystal field.

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Regional rule for the optical activity of conformational isomers of octahedral transition metal complexes

Cited by 79 publications

References 4 publications

The phenomenon of conglomerate crystallization. Part 40: The crystallization behavior oftrans- Co(III) amines (+)546-trans-[Co(3,2,3-tet)(NO2)2]Cl·3H2O (I), (−)589 -trans-[Co(3,2,3-tet)Cl2]NO3 (II), and of (+)546-trans-[Co(3,2,3-tet)(NO2)2]NO3 (III)

The phenomenon of conglomerate crystallization. Part 40: The crystallization behavior oftrans- Co(III) amines (+)546-trans-[Co(3,2,3-tet)(NO2)2]Cl·3H2O (I), (−)589 -trans-[Co(3,2,3-tet)Cl2]NO3 (II), and of (+)546-trans-[Co(3,2,3-tet)(NO2)2]NO3 (III)

The phenomenon of conglomerate crystallization. XXXV. The crystallization behaviour of {cis-α-Co(trien)ox]Cl}2·9H2O (1), cis-β-Co(3,2,3-tet)ox]Cl·4H2O(2), {cis-α-Co(trien)ox]NO3}2· H2O (3), and [mer-Co(dien)ox (NO2)] (4)

The crystal and molecular structures of dichloro(N¹ ,Ν¹ -dimethyl-(S)-1,2-propanediamine)- palladium(II) hemihydrate and dichloro(N¹,N¹- diethyl-(S)-1,2-propanediamine) palladium(II)

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Regional rule for the optical activity of conformational isomers of octahedral transition metal complexes

Cited by 79 publications

References 4 publications

The phenomenon of conglomerate crystallization. Part 40: The crystallization behavior oftrans- Co(III) amines (+)546-trans-[Co(3,2,3-tet)(NO2)2]Cl·3H2O (I), (−)589 -trans-[Co(3,2,3-tet)Cl2]NO3 (II), and of (+)546-trans-[Co(3,2,3-tet)(NO2)2]NO3 (III)

The phenomenon of conglomerate crystallization. Part 40: The crystallization behavior oftrans- Co(III) amines (+)546-trans-[Co(3,2,3-tet)(NO2)2]Cl·3H2O (I), (−)589 -trans-[Co(3,2,3-tet)Cl2]NO3 (II), and of (+)546-trans-[Co(3,2,3-tet)(NO2)2]NO3 (III)

The phenomenon of conglomerate crystallization. XXXV. The crystallization behaviour of {cis-α-Co(trien)ox]Cl}2·9H2O (1), cis-β-Co(3,2,3-tet)ox]Cl·4H2O(2), {cis-α-Co(trien)ox]NO3}2· H2O (3), and [mer-Co(dien)ox (NO2)] (4)

The crystal and molecular structures of dichloro(N1 ,Ν1 -dimethyl-(S)-1,2-propanediamine)- palladium(II) hemihydrate and dichloro(N1,N1- diethyl-(S)-1,2-propanediamine) palladium(II)

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The crystal and molecular structures of dichloro(N¹ ,Ν¹ -dimethyl-(S)-1,2-propanediamine)- palladium(II) hemihydrate and dichloro(N¹,N¹- diethyl-(S)-1,2-propanediamine) palladium(II)