Catalano V J, Kar H M, Bennett B L
Department of Chemistry, University of Nevada, Reno, Reno, Nevada 89557.
Inorg Chem. 2000 Jan 10;39(1):121-7. doi: 10.1021/ic9908827.
In acetonitrile the rigid diphosphine ligand 2,9-bis(diphenylphosphino)-1,8-naphthyridine (dppn) reacts with (SMe2)AuCl in the presence of NaPF6 to produce a pale-yellow material identified as Au2Na(mu-dppn)33 (1). In acetonitrile dppn reacts with 2 equiv of (SMe2)AuCl to form the simple Au-Cl adduct of the ligand, Au2Cl2dppn (2). In a fashion analogous to that of the synthesis of 1, the reaction of equimolar AgNO3 with dppn produces the trimetallic species Ag2(mu-dppn)3Ag3 (3) as a bright-yellow material. 1, 2, and 3 were characterized by 31P(1H) NMR spectroscopy, electronic absorption spectroscopy, X-ray crystallography, emission spectroscopy, and elemental analysis. Additionally 1 was further characterized by cyclic voltammetry and mass spectrometry. 1.4.5CH3CN.0.5(C2H5)2O (C107H72Au2F18N10.5NaO) crystallizes in the triclinic space group P1 with a = 15.408(3) A, b = 17.295(3) A, c = 22.425(5) A, alpha = 73.68(1) degrees, beta = 77.32(1) degrees, gamma = 74.18(1) degrees, V = 5451.4(19) A3, and Z = 2. C32H24Au2Cl2N2P2 (2) crystallizes in the monoclinic space group Cc with a = 10.936(2) A, b = 19.860(5) A, c = 20.864(2) A, beta = 118.182(1) degrees, V = 3127.3(8) A3, and Z = 4. Compound 3 crystallizes as the bis-DMSO adduct (C101H84Cl2F18N6O2P9S2) in the monoclinic space group C2/c with a = 28.825(7) A, b = 17.013(3) A, c = 23.916(7) A, beta = 115.23(1) degrees, V = 10609.6(44) A3, and Z = 4. The structures of 1 and 3 contain a three-coordinate metal capping the metallocryptate with an encapsulated ion. The central Ag(I) ion in 3 is positioned off-center to form a short Ag...Ag interaction of 3.145(2) A, while the central Na+ ion of 1 is centrally positioned with long Au...Na interactions of approximately 3.5 A. The solution-state properties of 1 were probed. 1 is emissive, as are the Li, K, and Cs analogues.
在乙腈中，刚性双膦配体2,9 - 双（二苯基膦基）-1,8 - 萘啶（dppn）在NaPF6存在下与（SMe2）AuCl反应，生成一种淡黄色物质，鉴定为Au2Na(μ - dppn)33（1）。在乙腈中，dppn与2当量的（SMe2）AuCl反应，形成配体的简单Au - Cl加合物Au2Cl2dppn（2）。与合成1的方式类似，等摩尔的AgNO3与dppn反应生成三金属物种Ag2(μ - dppn)3Ag3（3），为亮黄色物质。通过31P(1H)核磁共振光谱、电子吸收光谱、X射线晶体学、发射光谱和元素分析对1、2和3进行了表征。此外，通过循环伏安法和质谱对1进行了进一步表征。1.4.5CH3CN.0.5(C2H5)2O（C107H72Au2F18N10.5NaO）在三斜空间群P1中结晶，a = 15.408(3) Å，b = 17.295(3) Å，c = 22.425(5) Å，α = 73.68(1)°，β = 77.32(1)°，γ = 74.18(1)°，V = 5451.4(19) Å3，Z = 2。C32H24Au2Cl2N2P2（2）在单斜空间群Cc中结晶，a = 10.936(2) Å，b = 19.860(5) Å，c = 20.864(2) Å，β = 118.182(1)°，V = 3127.3(8) Å3，Z = 4。化合物3以双 - DMSO加合物（C101H84Cl2F18N6O2P9S2）的形式在单斜空间群C2/c中结晶，a = 28.825(7) Å，b = 17.013(3) Å，c = 23.916(7) Å，β = 115.23(1)°，V = 10609.6(44) Å3，Z = 4。1和3的结构包含一个三配位金属，其覆盖着带有包封离子的金属穴合物。3中的中心Ag(I)离子偏离中心位置，形成3.145(2) Å的短Ag...Ag相互作用，而1中的中心Na+离子位于中心位置，具有约3.5 Å的长Au...Na相互作用。对1的溶液态性质进行了探究。1具有发射性，其锂、钾和铯类似物也具有发射性。
