• Bulletin of the Korean Chemical Society
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• 제33권1호
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• pp.325-328
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• 2012

• Bulletin of the Korean Chemical Society
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• 제32권10호
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• pp.3783-3786
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• 2011

• Bulletin of the Korean Chemical Society
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• 제32권12호
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• pp.4361-4365
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• 2011

The nucleophilic substitution reactions of bis(N,N-dimethylamino) phosphinic chloride (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $65.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The magnitudes of ${\rho}_X$ (= -6.42) and ${\beta}_X$ (= 2.27) values are exceptionally great. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.69-0.96). A concerted $S_N2$ mechanism involving a backside attack is proposed on the basis of secondary inverse DKIEs and the variation trend of the $k_H/k_D$ values with X. The anilinolyses of six phosphinic chlorides in MeCN are briefly reviewed by means of DKIEs, steric effects of the two ligands, positive charge of the reaction center phosphorus atom, and selectivity parameters to obtain systematic information on phosphoryl transfer reaction mechanism.

• Bulletin of the Korean Chemical Society
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• 제32권3호
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• pp.889-893
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• 2011

The energetics and transition state (TS) structures of the reactions of six substrates, $R_1R_2P$(=O or S)Cl-type where $R_1=R_2$=Me and/or MeO, with ammonia in acetonitrile are theoretically investigated at the level of CPCM-MP2/6-31+G(d) and CPCM-MP2/6-311+G(3df,2p). The degrees of distortion of TS from the ideal trigonal bipyramidal pentacoordinate, ${\Delta}{{\delta}}_{{\neq}b}$ for a backside and ${\Delta}{{\delta}}_{{\neq}f}$ for a frontside attack, are calculated. The results of calculation suggest that the feasibility of a frontside attack for P=S is greater than that for P=O system when the two ligands, $R_1$ and $R_2$, becomes larger. The experimental and calculated results of anilinolyses of $R_1R_2P$(=O or S)Cl-type show the consistent tendencies.

• Bulletin of the Korean Chemical Society
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• 제33권3호
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• pp.1089-1092
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• 2012

• Bulletin of the Korean Chemical Society
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• 제32권4호
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• pp.1375-1378
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• 2011

• Bulletin of the Korean Chemical Society
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• 제31권12호
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• pp.3856-3859
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• 2010

• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.1945-1950
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• 2011

The pyridinolysis of methyl phenyl phosphinic chloride is investigated kinetically in acetonitrile at -20.0 $^{\circ}C$. The Hammett and Br${\o}$nsted plots for substituent X variations in the nucleophiles are biphasic concave downwards with a break point at X = H, and unusual positive ${\rho}_X$ (= 2.94) and negative ${\beta}_X$ (= -0.48) values are obtained for the strongly basic nucleophiles. A stepwise mechanism with a rate-limiting step change from bond breaking for the weakly basic pyridines to bond formation for the strongly basic pyridines is proposed on the basis of biphasic concave downward Hammett and Br${\o}$nsted plots. Unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are rationalized by the isokinetic relationship. The pyridinolyses and anilinolyses of four $R_1R_2$P(=O)Cl-type substrates, dimethyl, diethyl, methyl phenyl, and diphenyl phosphinic chlorides in acetonitrile are compared to obtain systematic information on phosphoryl transfer reaction mechanism. The combination of the two ligands, Me and Ph, shows unexpected kinetic results for both the anilinolysis and pyridinolysis: greatest magnitude of $k_H/k_D$ (= 2.10) involving deuterated anilines $[XC_6H_4NH_2(D_2)]$ for the anilinolysis, and exceptionally fast rate and biphasic concave downward free energy correlation for the pyridinolysis.

• Bulletin of the Korean Chemical Society
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• 제35권3호
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• pp.753-757
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• 2014

The nucleophilic substitution reactions of Y-aryl N,N-dimethyl phosphoroamidochloridates with substituted anilines and deuterated anilines are kinetically investigated in acetonitrile at $65.0^{\circ}C$. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed based on the positive ${\rho}_{XY}$ value. The deuterium kinetic isotope effects involving deuterated anilines show secondary inverse with all the nucleophiles, rationalized by a dominant backside nucleophilic attack.

• Bulletin of the Korean Chemical Society
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• 제32권11호
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• pp.3880-3886
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• 2011

The nucleophilic substitution reactions of diisopropyl thiophophinic chloride (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $65.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.80-0.96). The anilinolyses of ten P=S systems in MeCN are reviewed on the basis of DKIEs and selectivity parameters to obtain systematic information on the DKIEs and mechanism for thiophosphoryl transfer reactions. The steric effects of the two ligands on reactivity, DKIEs, mechanism, and substituent effects of the nucleophile (X) on the DKIEs are discussed.