Additions and corrections

Balt, S.; Gamelkoorn, Hendrikus J.

doi:10.1039/dt9850002223

Cited by 4 publications

(9 citation statements)

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“…The concern 10 was not with the isotope effect per se, but rather the converse, using the observed kinetic isotope effect to determine the preferred site of deuteration in the parent complex. Our re-examination of the isotope effect for the acid hydrolysis of the trans -azido-dmso complex, reported herein, yielded quite different results, and they undermine the previous basis for the assignment of the two different sets of NH protons in the NMR spectra.…”

Section: Introductioncontrasting

confidence: 75%

“…An unprecedented rearrangement of this trans -[Co(en) 2 (OSMe 2 )(N 3 )] 2+ species in which an en chelate is rotated through 180° during base catalyzed solvolysis in NH 3 (l), Figure , has also been claimed 4 Proposed rearrangement for the base catalyzed substitution of trans -[Co(en) 2 (OSMe 2 )(N 3 )] 2+ in NH 3 (l). …”

Section: Introductionmentioning

confidence: 97%

“…Our work on the [Co(NH 3 ) 5 Cl] 2+ system was motivated by the study of the aquation of selectively deuterated trans -[Co(en) 2 (OSMe 2 )(N 3 )] 2+ complexes. N-Perdeuteration was reported to reduce the aquation rate by ca.…”

Section: Introductionmentioning

confidence: 99%

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Secondary Deuterium Kinetic Isotope Effect for Aquation, Solvolysis, and Isomerization Reactions of trans-[Co(en)₂(OSMe₂)N₃]²⁺, and the Resolution of a Mechanistic Anomaly

Jackson

2004

Inorg. Chem.

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The two closely spaced NH signals in the (1)H NMR spectrum of trans-[Co(en)(2)(OSMe(2))(N(3))](2+) have been reassigned using 2D NMR and other techniques. Thus, the unusual syn to anti (to Co-N(3)) NH rearrangement on base catalyzed substitution of the selectively deuterated complex in ND(3)(l) has been reinterpreted as "normal", with inversion of the effective deprotonation site accompanying the act of substitution. The re-examination of this system required a repeat study of the secondary isotope effect for the acid hydrolysis reaction, previously used to assign syn and anti amine sites, and this has been extended to other solvents (Me(2)SO, MeCN). The relative NH proton exchange rates are also reconsidered. A systematic rate reduction for Me(2)SO substitution is observed for deuterium incorporation into the cis-NH centers, irrespective of whether these are syn or anti, and the effect is much greater in Me(2)SO than in water. The results are interpreted in terms of zero point energy effects and coupled vibrations.

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Section: Introductioncontrasting

confidence: 75%

Section: Introductionmentioning

confidence: 97%

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Secondary Deuterium Kinetic Isotope Effect for Aquation, Solvolysis, and Isomerization Reactions of trans-[Co(en)₂(OSMe₂)N₃]²⁺, and the Resolution of a Mechanistic Anomaly

Jackson

2004

Inorg. Chem.

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“…P2(CHF2)4 + HC1 -(CHF2)2PC1 + (CHF2)2PH (5) with P2(CF3)4 not expected to resist a catalytic environment.4…”

Section: New Diphosphinesmentioning

confidence: 99%

New chemistry of (difluoromethyl)phosphines

Burg¹

1985

Inorg. Chem.

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“…Our interest in the kinetic isotope effect for hydrolysis reactions stems from a paper by Balt and Gamelkoorn on the ammoniolysis of an elusive complex we synthesized in 1976, trans -[Co(en) 2 (N 3 )(OSMe 2 )] 2+ . This ion has two distinct kinds of NH protons, one adjacent to the azide ligand and one remote .…”

Section: Introductionmentioning

confidence: 99%

Stereoselectivity of the Secondary Isotope Effect in the Aquation of [Co(NH₃)₅Cl]²⁺

Jackson

2002

Inorg. Chem.

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A careful kinetic study of the acid hydrolysis of [Co(NH(3))(5)Cl](2+) and the selectively deuterated species trans-[Co(NH(3))(4)(ND(3))Cl](2+), trans-[Co(ND(3))(4)(NH(3))Cl](2+), and [Co(ND(3))(5)Cl](2+) reveals that N-deuteration reduces the hydrolysis rate at both the cis and trans sites. On a per-D basis, the rate reduction is three times more effective for trans-Cl deuteration. This result is contrary to conventional wisdom but has never been tested previously. It appears to be the first example of significant stereoselectivity for the secondary isotope effect in a substitution reaction, in either inorganic or organic systems. An explanation is offered in terms of the effect of D-substitution on zero point energies, the different extents of coupling of NH(D) and Co-Cl vibrational modes according to their stereochemical relationship, and the view that the rate of acid hydrolysis of the [Co(NH(3))(5)Cl](2+) involves an aberrant Co-Cl vibration component.

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Additions and corrections

Cited by 4 publications

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Secondary Deuterium Kinetic Isotope Effect for Aquation, Solvolysis, and Isomerization Reactions of trans-[Co(en)₂(OSMe₂)N₃]²⁺, and the Resolution of a Mechanistic Anomaly

Secondary Deuterium Kinetic Isotope Effect for Aquation, Solvolysis, and Isomerization Reactions of trans-[Co(en)₂(OSMe₂)N₃]²⁺, and the Resolution of a Mechanistic Anomaly

New chemistry of (difluoromethyl)phosphines

Stereoselectivity of the Secondary Isotope Effect in the Aquation of [Co(NH₃)₅Cl]²⁺

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Additions and corrections

Cited by 4 publications

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Secondary Deuterium Kinetic Isotope Effect for Aquation, Solvolysis, and Isomerization Reactions of trans-[Co(en)2(OSMe2)N3]2+, and the Resolution of a Mechanistic Anomaly

Secondary Deuterium Kinetic Isotope Effect for Aquation, Solvolysis, and Isomerization Reactions of trans-[Co(en)2(OSMe2)N3]2+, and the Resolution of a Mechanistic Anomaly

New chemistry of (difluoromethyl)phosphines

Stereoselectivity of the Secondary Isotope Effect in the Aquation of [Co(NH3)5Cl]2+

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Secondary Deuterium Kinetic Isotope Effect for Aquation, Solvolysis, and Isomerization Reactions of trans-[Co(en)₂(OSMe₂)N₃]²⁺, and the Resolution of a Mechanistic Anomaly

Secondary Deuterium Kinetic Isotope Effect for Aquation, Solvolysis, and Isomerization Reactions of trans-[Co(en)₂(OSMe₂)N₃]²⁺, and the Resolution of a Mechanistic Anomaly

Stereoselectivity of the Secondary Isotope Effect in the Aquation of [Co(NH₃)₅Cl]²⁺