Benny Paul D, Barnes Charles L, Piekarski Pamela M, Lydon John D, Jurisson Silvia S
The Chemistry Department, University of Missouri, Columbia, Missouri 65211, USA.
Inorg Chem. 2003 Oct 6;42(20):6519-27. doi: 10.1021/ic030240q.
Several rhenium(V) oxo complexes with tetradentate N(2)O(2) Schiff base ligands were synthesized and characterized. The general synthetic procedure involved reaction of [NBu(4)][ReOCl(4)] with a tetradentate Schiff base ligand (L(1) = N,N'-ethylenebis(acetylacetoneimine), (acac(2)en) or L(2) = N,N'-propylenebis(acetylacetoneimine) (acac(2)pn)) in ethanol solution to generate complexes of the form trans-ReOX(L) where X = Cl(-), MeO(-), ReO(4)(-), or H(2)O. The product isolated from the reaction was found to be dependent on the reaction conditions, in particular the presence or absence of water and/or base. The mu-oxo-Re(2)O(3)(L)(2) dimers were synthesized and characterized for chemical and structural comparison to the related monomers. Conversion of the monomer to its dimer analogue was followed qualitatively by spectrophotometry. The complexes were characterized by (1)H and (13)C NMR, UV-vis, and IR spectroscopy, elemental analysis, and single crystal X-ray diffraction. The crystallographic data reported for the structures are as follows: trans-[ReO(OH(2))(acac(2)en)]Cl (H(20)C(12)ClN(2)O(4)Re) 1, triclinic (Ponemacr;), a = 7.2888(6) A, b = 9.8299(8) A, c = 10.8195(9) A, alpha = 81.7670(10) degrees, beta = 77.1510(10) degrees, gamma = 87.6200(10) degrees, V = 747.96(11) A(3), Z = 2; trans-[ReO(OReO(3))(acac(2)en)] (H(18)C(12)N(2)O(7)Re(2)) 2, monoclinic (P2(1)/c), a = 7.5547(4) A, b = 8.7409(5) A, c= 25.7794(13) A, beta = 92.7780(10) degrees, V = 1700.34(16) A(3), Z = 4; trans-[ReOCl(acac(2)pn)] (H(20)C(13)N(2)O(3)ClRe) 3, monoclinic (P2(1)/c), a = 8.1628(5) A, b = 13.0699(8) A, c = 28.3902(17) A, beta = 97.5630(10) degrees, V = 3002.5(3) A(3), Z = 8; trans-[ReO(OMe)(acac(2)pn)] (H(23)C(14)N(2)O(4)Re) 4, monoclinic (P2(1)/c), a = 6.7104(8) A, b = 27.844(3) A, c = 8.2292(9) A, beta = 92.197(2) degrees, V = 1536.4(3) A(3), Z = 4; trans-[mu-oxo-Re(2)O(3)(acac(2)en)(2)] (H(36)C(24)N(4)O(7)Re(2)) 5, monoclinic (P2(1)/n), a = 9.0064(5) A, b = 12.2612(7) A, c = 12.3695(7) A, beta = 90.2853(10) degrees, V = 1365.94(13) A(3), Z = 2; and trans-[mu-oxo Re(2)O(3)(acac(2)pn)(2)] (H(40)C(26)N(4)O(7)Re(2)) 6, monoclinic (P2(1)/n), a = 9.1190(5) A, b = 12.2452(7) A, c = 12.8863(8) A, beta = 92.0510(10) degrees, V = 1438.01(14) A(3), Z = 2.
合成并表征了几种含四齿N(2)O(2)席夫碱配体的铼(V)氧配合物。一般的合成步骤包括在乙醇溶液中使[四丁基铵][高铼酸氯]与四齿席夫碱配体（L(1) = N,N'-亚乙基双(乙酰丙酮亚胺)，(acac(2)en)或L(2) = N,N'-亚丙基双(乙酰丙酮亚胺) (acac(2)pn)）反应，生成反式-ReOX(L)形式的配合物，其中X = Cl(-)、MeO(-)、ReO(4)(-)或H(2)O。发现从反应中分离出的产物取决于反应条件，特别是水和/或碱的存在与否。合成并表征了μ-氧代-Re(2)O(3)(L)(2)二聚体，以便与相关单体进行化学和结构比较定性。通过分光光度法跟踪单体向其二聚体类似物的转化。通过(1)H和(13)C NMR、紫外可见光谱、红外光谱、元素分析和单晶X射线衍射对配合物进行了表征。所报道结构的晶体学数据如下：反式-[ReO(OH(2))(acac(2)en)]Cl (H(20)C(12)ClN(2)O(4)Re) 1，三斜晶系（P1），a = 7.2888(6) Å，b = 9.8299(8) Å，c = 10.8195(9) Å，α = 81.7670(10)°，β = 77.1510(10)°，γ = 87.6200(10)°，V = 747.96(11) Å(3)，Z = 2；反式-[ReO(OReO(3))(acac(2)en)] (H(18)C(12)N(2)O(7)Re(2)) 2，单斜晶系（P2(1)/c），a = 7.5547(4) Å，b = 8.7409(5) Å，c = 25.7794(13) Å，β = 92.7780(10)°，V = 1700.34(16) Å(3)，Z = 4；反式-[ReOCl(acac(2)pn)] (H(20)C(13)N(2)O(3)ClRe) 3，单斜晶系（P2(1)/c），a = 8.1628(5) Å，b = 13.0699(8) Å，c = 28.3902(17) Å，β = 97.5630(10)°，V = 3002.5(3) Å(3)，Z = 8；反式-[ReO(OMe)(acac(2)pn)] (H(23)C(14)N(2)O(4)Re) 4，单斜晶系（P2(1)/c），a = 6.7104(8) Å，b = 27.844(3) Å，c = 8.2292(9) Å，β = 92.197(2)°，V = 1536.4(3) Å(3)，Z = 4；反式-[μ-氧代-Re(2)O(3)(acac(2)en)(2)] (H(36)C(24)N(4)O(7)Re(2)) 5，单斜晶系（P2(1)/n），a = 9.0064(5) Å，b = 12.2612(7) Å，c = 12.3695(7) Å，β = 90.2853(10)°，V = 1365.94(13) Å(3)，Z = 2；以及反式-[μ-氧代Re(2)O(3)(acac(2)pn)(2)] (H(40)C(26)N(4)O(7)Re(2)) 6，单斜晶系（P2(1)/n），a = 9.1190(5) Å，b = 12.2452(7) Å，c = 12.8863(8) Å，β = 92.0510(10)°，V = 1438.01(14) Å(3)，Z = 2。
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