Synthesis and Characterization of Substituted Pyridine Complexes of Molybdenum(Ⅴ). Di-${\mu}$-oxo-dioxodichlorobis(substituted pyridines) dimolybdenum(Ⅴ) and Substituted Pyridinium Di-${\mu}$-oxo-dioxohexaisothiocyanatodimolybdates(Ⅴ)

몰리브덴의 피리딘계 착물합성과 그 성질 (제5보). 이-${\mu}$ -옥소-이옥소이클로로비스(치환피리딘) 이 몰리브덴 (Ⅴ) 와 이-${\mu}$- 옥소-이옥소육이소티오시아나토 이 몰리브덴 (Ⅴ) 산 치환피리딘늄

  • Kim, Chang-Su (Department of Chemistry, College of Education, Daegu University) ;
  • Sang Oh Oh (Department of Chemistry, Kyungpook National University)
  • 김창수 (대구대학교 사범대학 화학과) ;
  • 오상오 (경북대학교 자연과학대학 화학과)
  • Published : 1982.12.30

Abstract

$Mo_2O_4Cl_2$$(X-py)_4{\cdot}2H_2$O and $(X-pyH)_4$[$Mo_2O_4(NCS)_6)$]${\cdot}H_2$O have been prepared. The infrared, electronic and reflectance spectra, molar conductances and magnetic susceptibility data of complexes are reported. $Mo_2O_4Cl_2$$(X-py)_4{\cdot}2H_2$O (X-py were 3-and 4-cyanopyridine, nicotinamide, 3,5-lutidine and 2-amino-4-picoline) were obtained by hydrolysis of the corresponding substituted pyridinium oxopentachloromolybdates(Ⅴ). Addition of water and substituted pyridines to molybdenum(Ⅴ)-thiocyanate ethylacetate extract yielded brown compounds, $(X-pyH)_4$[$Mo_2O_4(NCS)_6)$]${\cdot}H_2$O where X-py were pyridine, ${\alpha}$, 3-bromopyridine 3,5-lutidine, 3-benzoylpyridine and 4-acetylpyridine. Binuclear, $Mo_2O_4Cl_2(X-py)_4{\cdot}2H_2$ prepared from hydrolysis of $(X-pyH)_2[MoOCl_5]{\cdot}H_2O$ were diamagnetic and nonelectrolytes. The anion of $(X-pyH)_4$[$Mo_2O_4(NCS)_6)$]${\cdot}H_2$O was formulated as dimer and electrolyte.

$Mo_2O_4Cl_2$$(X-py)_4{\cdot}2H_2$O와 $(X-pyH)_4$[$Mo_2O_4(NCS)_6)$]${\cdot}H_2$O를 합성하고 이들 착물에 대한 자기적 및 분광학적성질을 조사하였다. $Mo_2O_4Cl_2$$(X-py)_4$·$2H_2$O (X-py=3-및 4-시아노피리딘, 2-및 4-아미노피리딘, 니코틴아미드, 3,5-루티딘 및 2-아미노-4-피코린)은 옥소오클로로몰리브덴(Ⅴ)산 치환피리딘늄을 가수분해시켜 얻었다. 또한, MoO(NCS)$_3$에 물과 치환피리딘류를 가하여 갈색의 $(X-pyH)_4$[$Mo_2O_4(NCS)_6)$]$H_2$O를 얻었다. 여기서 X-py는 피리딘,${\alpha}$-피코린, 3-브로모피리딘, 3,5-루피린, 3-벤조일피리딘 및 4-아세틸피리딘이다. $Mo_2O_4Cl_2$$(X-py)_4{\cdot}2H_2$O와 $(X-pyH)_4$[$Mo_2O_4(NCS)_6)$]${\cdot}H_2$O는 반자성을 가진 이합체로서 $Mo_2O_4Cl_2(X-py)_4{\cdot}2H_2$O는 비전해질이나 $(X-pyH)_4$[$Mo_2O_4(NCS)_6)$]${\cdot}H_2$O는 전해착물임을 알았다.

Keywords

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