Computational Studies of Relative Stabilities of Low-Spin d6 cis- and trans-[M(en)2X2]+ Complexes (M = Co, Rh, Ir): Steric and Electronic Effects in the Context of the Structural Trans Influence

2019 ◽  
Vol 123 (12) ◽  
pp. 2438-2446
Author(s):  
Noel A. Amaro ◽  
Keith R. Ammerman ◽  
Devon J. Boland ◽  
Cory J. Bork ◽  
Justin V. Davis ◽  
...  
Keyword(s):  
Computational Studies ◽  
Electronic Effects ◽  
Relative Stabilities ◽  
Trans Influence ◽  
Cis And Trans

An inverse, linear correlation of cis and trans influence

1974 ◽  
Vol 10 (5) ◽  
pp. 373-376 ◽  
Author(s):  
Keith R. Dixon ◽  
Kenneth C. Moss ◽  
Martin A.R. Smith
Keyword(s):  
Linear Correlation ◽  
Trans Influence ◽  
Cis And Trans

Factors controlling the relative stabilities of cis- and trans-[PtX2L2] isomers: Chatt and Wilkins—50 years on

2002 ◽  
pp. 278-279 ◽  
Author(s):  
Jeremy N. Harvey ◽  
Katie M. Heslop ◽  
A. Guy Orpen ◽  
Paul G. Pringle
Keyword(s):  
Relative Stabilities ◽  
Cis And Trans

[1H,15N] N.M.R. Kinetic Studies of Reactions of cis- and trans-[PtCl2(15NH3)(c-C6H1115NH2)] with Guanosine 5'-Monophosphate

1999 ◽  
Vol 52 (3) ◽  
pp. 173 ◽  
Author(s):  
Sarah J. Barton ◽  
Kevin J. Barnham ◽  
Abraha Habtemariam ◽  
Urban Frey ◽  
Rodney E. Sue ◽  
...  
Keyword(s):  
Trans Isomer ◽  
Active Metabolite ◽  
Kinetic Studies ◽  
Trans Influence ◽  
Trans Complex ◽  
Kinetics Of Reaction ◽  
Cis And Trans ◽  
Kinetics Of ◽  
Cis Isomer ◽  
Amine Ligand

cis-[PtCl2(15NH3)(c-C6H11NH2)] is an active metabolite of the oral platinum(IV) anticancer drug cis,trans,cis-[PtCl2(CH3CO2)2(NH2)(c-C6H11NH2)]. Since it is likely that guanine bases on DNA are targets for this drug, we have analysed the kinetics of reaction of this platinum(II) metabolite with guanosine 5′-monophosphate (5′-GMP) at 310 K, pH 7, using [1H, 15N] n.m.r. methods. Reactions of the trans isomer are reported for comparison. The reactions proceed via aquated intermediates, and, for the cis isomer, the rates of aquation and substitution of H2O by 5′-GMP are 2-5 times faster trans to the amine ligand (c-C6H11NH2) compared to trans to NH3 for both the first and second steps. For the trans complex, the first aquation step is c. 3 times faster than for the cis complex, as expected from the higher trans influence of Cl¯, whereas the rate of the second aquation step (trans to N7 of 5′-GMP) is comparable to that trans to NH3. These findings have implications for the courses of reactions with DNA.

scholarly journals Substituenteneinflüsse auf die 13C–NMR-chemischen Verschiebungen cis- und trans-konfigurierter Trimethincyanine / Substituent Effects on the 13C NMR Chemical Shifts of Trimethincyanines with cis and trans Configuration

1976 ◽  
Vol 31 (12) ◽  
pp. 1641-1645 ◽  
Author(s):  
Walter Grahn
Keyword(s):  
13C Nmr ◽  
Chemical Shifts ◽  
Substituent Effects ◽  
Electron Systems ◽  
Coupling Constant ◽  
Electronic Effects ◽  
Nmr Chemical Shifts ◽  
Monosubstituted Benzenes ◽  
Cis And Trans ◽  
C Nmr

The 13C NMR chemical shifts of fifteen 6 substituted 2,3-dihydro-1,4-diazepinium salts (cis trimethincyanines) (1) and twelve 2 substituted bis(dimethylamino)trimethinium salts (trans trimethincyanines) (2) have been determined. A comparison of the substituentinduced shifts (13C SCS) of 1 and 2 allows no distinction between steric and electronic effects. In the three 6 п-electron systems 1, 2 and monosubstituted benzenes the 13C SCS are similar for the substituent bearing carbon atoms. A surprisingly large 4JFCCNC coupling constant has been observed.

13C Nuclear Magnetic Resonance Studies of Organometallic Compounds. IV. cis-Dimethylplatinum(II) Derivatives

1974 ◽  
Vol 52 (7) ◽  
pp. 1165-1170 ◽  
Author(s):  
Howard Charles Clark ◽  
Leo Ernest Manzer ◽  
John Edward Henry Ward
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Organometallic Compounds ◽  
Methyl Groups ◽  
Magnetic Resonance Studies ◽  
Trans Influence ◽  
13C Nuclear Magnetic Resonance ◽  
Cis And Trans ◽  
Derivatives Of ◽  
Nuclear Magnetic

Data derived from the 13C n.m.r. spectra of seven neutral cis-dimethylplatinum(II) derivatives of the type cis-(CH3)2PtL2 and cis-(CH3)2Pt(L—L) (where L and L—L are neutral donors) are discussed and compared with data derived from the 1H n.m.r. spectra of the complexes. Simultaneous variations in L or L—L reveal that the n.m.r. trans-influence rather than the n.m.r. cis-influence is dominant. The suggestion that the n.m.r. cis- and trans-influences may be additive is discussed. In contrast with data obtained by other workers, it is shown that the 1JCH values of the platinum methyl groups are essentially insensitive to variations in the remaining ligands.

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