Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Novel Counter Ion Effect on the Disruption of the Homobimetallic Anion,$ (\eta^5-MeCp)Mn(CO)_2Mn(CO)_5-M^+ (M^+=Na^+, PPN^{+a}) by PR_3 (R=C_6H_5,\; C_2H_5,\; OCH_3)$

  • Published : 1998.04.20
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Abstract

The homobimetallic anion, $({\eta}^5-MeCp)Mn(CO)_2Mn(CO)_5-M^+\; (M^+=Na^+, PPN^+$) was disrupted by $PR_3\;(R=C_6H_5,\;C_2H_5,\;OCH_3)$ in THF at various temperatures (r.t. ∼65℃) under the pseudo first order reaction conditions where excess of $PR_3$ was employed under a nitrogen atmosphere. For the reaction involving $PPN^+$ analog, Mn-Mn heterolytic cleavage occurred, leading to $PPN^+Mn(CO)_5^-\; and \;({\eta}^5-MeCp)Mn(CO)_2PR_3$ as products; however, in case of $Na^+\; analog,\; Na^+$ seems to play a novel counter ion effect on the disruption reaction by transferring one terminal CO from the $Mn(CO)_5$ moiety on to the $({\eta}^5-MeCp)Mn(CO)_2$ of the corresponding homobimetallic complex, eventually resulting in $Na^+Mn(CO)_4PR_3^-\;and\;({\eta}^5-MeCp)Mn(CO)_3$. This reaction is of overall first order with respect to [homobimetallic complex] with the activation parameters (ΔH≠=23.0±0.7 kcal/mol, ΔS≠= - 8.7±0.8 e.u. for $Na^+$ analog; ΔH≠=28.8±0.4 kcal/mol, ΔS≠=15.7±0.6 e.u. for $PPN^+$ analog reaction).

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References

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