A Functionalized Ag2S Molecular Architecture: Facile Assembly of the Atomically Precise Ferrocene‐Decorated Nanocluster [Ag74S19(dppp)6(fc(C{O}OCH2CH2S)2)18]

A ferrocene‐based dithiol 1,1′‐[fc(C{O}OCH₂CH₂SH)₂] has been prepared and treated with a Ag^I salt to form the stable dithiolate compound [fc(C{O}OCH₂CH₂SAg)₂]_n (fc=[Fe(η⁵‐C₅H₄)₂]). This is used as a reagent for the preparation of the nanocluster [Ag₇₄S₁₉(dppp)₆(fc(C{O}OCH₂CH₂S)₂)₁₈] which was obtained in good yield (dppp=1,3‐bis(diphenylphosphino)propane).     

簇合物[(WS4)2Ag4(dppm)3]·Py·DMF的低加热固相合成与晶体结构

通过低加热固相合成法制备了六核簇合物[(WS4)2Ag4(dppm)3]·Py·DMF,用单晶X-射线衍射法测得该晶体属单斜晶系,空间群P21/c,晶胞参数a＝2.2990(4),b＝1.4094(2),c＝2.8083(5)nm,β＝107.472(2)°,V＝8.680(2)nm3,Z＝4,DC＝1.807 g/cm3,μ＝38.72 cm-1,F(000)＝4608,R＝0.0482,wR＝0.0987.[(WS4)2Ag4(dppm)3]的分子结构含有二个WS4Ag2簇单元和三个dppm配体,其中一个dppm配体连接同一WS4Ag2簇单元内的Ag(1)和Ag(2)原子,而另二个dppm配体则分别和不同WS4Ag2簇单元内的二个Ag原子桥联.     

Formation and chemical reactivities of a new type of double-butterfly [[Fe2(mu-CO)(CO)6]2(mu-SZS-mu)]2-: synthetic and structural studies on novel linear and macrocyclic butterfly Fe/E (E=S,Se) cluster complexes

A new type of double-butterfly [[Fe(2)(mu-CO)(CO)(6)](2)(mu-SZS-mu)](2-) (3), a dianion that has two mu-CO ligands, has been synthesized from dithiol HSZSH (Z=(CH(2))(4), CH(2)(CH(2)OCH(2))(1-3)CH(2)), [Fe(3)(CO)(12)], and Et(3)N in a molar ratio of 1:2:2 at room temperature. Interestingly, the in situ reactions of dianions 3 with various electrophiles affords a series of novel linear and macrocyclic butterfly Fe/E (E=S, Se) cluster complexes. For instance, while reactions of 3 with PhC(O)Cl and Ph(2)PCl give linear clusters [[Fe(2)(mu-PhCO)(CO)(6)](2)(mu-SZS-mu)] (4 a,b: Z=CH(2)(CH(2)OCH(2))(2,3)CH(2)) and [[Fe(2)(mu-Ph(2)P)(CO)(6)](2)(mu-SZS-mu)] (5 a,b: Z=CH(2)(CH(2)OCH(2))(2,3)CH(2)), reactions with CS(2) followed by treatment with monohalides RX or dihalides X-Y-X give both linear clusters [[Fe(2)(mu-RCS(2))(CO)(6)](2)(mu-SZS-mu)] (6 a-e: Z=CH(2)(CH(2)OCH(2))(1,2)CH(2); R=Me, PhCH(2), FeCp(CO)(2)) and macrocyclic clusters [[Fe(2)(CO)(6)](2)(mu-SZS-mu)(mu-CS(2)YCS(2)-mu)] (7 a-e: Z=(CH(2))(4), CH(2)(CH(2)OCH(2))(1-3)CH(2); Y=(CH(2))(2-4), 1,3,5-Me(CH(2))(2)C(6)H(3), 1,4-(CH(2))(2)C(6)H(4)). In addition, reactions of dianions 3 with [Fe(2)(mu-S(2))(CO)(6)] followed by treatment with RX or X-Y-X give linear clusters [[[Fe(2)(CO)(6)](2)(mu-RS)(mu(4)-S)](2)(mu-SZS-mu)] (8 a-c: Z=CH(2)(CH(2)OCH(2))(1,2)CH(2); R=Me, PhCH(2)) and macrocyclic clusters [[[Fe(2)(CO)(6)](2)(mu(4)-S)](2)(mu-SYS-mu)(mu-SZS-mu)] (9 a,b: Z=CH(2)(CH(2)OCH(2))(2,3)CH(2); Y=(CH(2))(4)), and reactions with SeCl(2) afford macrocycles [[Fe(2)(CO)(6)](2)(mu(4)-Se)(mu-SZS-mu)] (10 d: Z=CH(2)(CH(2)OCH(2))(3)CH(2)) and [[[Fe(2)(CO)(6)](2)(mu(4)-Se)](2)(mu-SZS-mu)(2)] (11 a-d: Z=(CH(2))(4), CH(2)(CH(2)OCH(2))(1-3)CH(2)). Production pathways have been suggested; these involve initial nucleophilic attacks by the Fe-centered dianions 3 at the corresponding electrophiles. All the products are new and have been characterized by combustion analysis and spectroscopy, and by X-ray diffraction techniques for 6 c, 7 d, 9 b, 10 d, and 11 c in particular. X-ray diffraction analyses revealed that the double-butterfly cluster core Fe(4)S(2)Se in 10 d is severely distorted in comparison to that in 11 c. In view of the Z chains in 10 a-c being shorter than the chain in 10 d, the double cluster core Fe(4)S(2)Se in 10 a-c would be expected to be even more severely distorted, a possible reason for why 10 a-c could not be formed.     

Niobium Alcoholate Clusters with an Octahedral Arrangement of Metal Atoms: [K(CH3OH)4]2 [Nb6(OCH3)18] and [Na([18]crown‐6)(C2H5OH)2]2 [Nb6(OC2H5)12(NCS)6]

Complete exchange : [M₆X₁₂] type cluster compounds with an octahedral M₆ metal atom arrangement, which is completely surrounded by alcoholato ligands, were unknown until now. The first representatives are prepared containing a [Nb₆(OR)₁₂]⁴⁺ unit (R=CH₃ or C₂H₅). They are accessible at elevated temperatures from strongly basic alcoholate solutions of [Nb₆Cl₁₂]²⁺‐containing precursors. C gray, H white, K turquoise, Nb blue, O red.

     

Copper(I) alkynyl clusters, [Cu(x+y)(hfac)(x)(C[triple chemical bond]CR)(y)], with Cu(10)-Cu(12) cores

The facile syntheses and the structures of five new Cu(I) alkynyl clusters, [Cu(12)(hfac)(8)(C[triple chemical bond]CnPr)(4)(thf)(6)]xTHF (1), [Cu(12)(hfac)(8)(C[triple chemical bond]CtBu)(4)] (2), [Cu(12)(hfac)(8)(C[triple chemical bond]CSiMe(3))(4)] (3), [Cu(10)(hfac)(6)(C[triple chemical bond]CtBu)(4)(diethyl ether)]/[Cu(10)(hfac)(6)(C[triple chemical bond]CtBu)(3)(C[triple chemical bond]CnPr)(diethyl ether)] (4) and [Cu(10)(hfac)(6)(C[triple chemical bond]CtBu)(4)(diethyl ether)] (5) are reported, in which hfacH=1,1,1,5,5,5-hexafluoropentan-2,4-dione. The first independent molecule found in the crystals of 4 (4 a) proved to be chemically identical to 5. The Cu(10) and Cu(12) cores in these clusters are based on a central "square" Cu(4)C(4) unit. Whilst the connectivities of the Cu(10) or Cu(12) units remain identical the geometries vary considerably and depend on the bulk of the alkynyl group, weak coordination of ether molecules to copper atoms in the core and CuO intramolecular contacts formed between Cu-hfac units on the periphery of the cluster. Similar intermolecular contacts and interlocking of Cu-hfac units are formed in the simple model complex [Cu(2)(hfac)(2)(HC[triple chemical bond]CtBu)] (6). When linear alkynes, C(n)H(2n+1)C[triple chemical bond]CH, are used in the synthesis and non-coordinating solvents are used in the workup, further association of the Cu(4)C(4) cores occurs and clusters with more than eighteen copper atoms are isolated.     

Synthesen und Strukturen der polymeren Silber‐Komplexe [Ag2Cl2(dppbp)3]∞, [Ag2(SPh)2(dppe)3]∞ und [Ag2(SPh)2(triphos)]∞ sowie der Silber‐Chalkogenido‐Cluster [Ag7(SPh)7(dppm)3], {[Ag7(TePh)7(dppp)3]2(dppp)} und [Ag22Cl(SPh)10(PhCOO)11(dmf)3]∞

Syntheses and Structures of the Polymeric Silver Complexes [Ag₂Cl₂(dppbp)₃]_∞, [Ag₂(SPh)₂(dppe)₃]_∞ and [Ag₂(SPh)₂(triphos)]_∞ as well as the Silver Chalcogenido Clusters [Ag₇(SPh)₇(dppm)₃], {[Ag₇(TePh)₇(dppp)₃]₂(dppp)}, and [Ag₂₂Cl(SPh)₁₀(PhCOO)₁₁(dmf)₃]_∞ The reaction of silver carboxylate with silylated chalcogen compounds have been found to have a possibility for the synthesis of metal‐chalcogenide‐custers. Especially phosphine ligands have been found to be useful in stabilising the cluster cores. Some of the silver carboxylate phosphine complexes, which are formed in‐situ, ([Ag₂Cl₂(dppbp)₃]_∞ ( 1 )) and some silver chalcogen complexes ([Ag₂(SPh)₂(dppe)₃]_∞ ( 2 ) und [Ag₂(SPh)₂(triphos)]_∞ ( 3 )), could be isolated and characterised by X‐ray diffraction. Using special reaction conditions, it is possible to isolate cluster species like [Ag₇(SPh)₇(dppm)₃] ( 4 ), {[Ag₇(TePh)₇(dppp)₃]₂(dppp)} ( 5 ) and [Ag₂₂Cl(SPh)₁₀(PhCOO)₁₁(dmf)₃]_∞ ( 6 ) beside the complex compounds. 1: Space group P2₁/n (No. 14), Z = 2, a = 1336, 1(2), b = 2081, 2(5), c = 2015, 4(4) pm, β = 99, 87(2)°; 2: Space group P2₁/n (No. 14), Z = 2, a = 1416, 1(3), b = 1874, 7(4), c = 1444, 8(3) pm, β = 93, 26(3)°; 3: Space group P2₁/n (No. 14), Z = 4, a = 1456, 8(3, b = 1890, 2(4), c = 1916, 1(4) pm, β = 99, 11(3)°; 4: Space group P2₁/n (No. 14), Z = 4, a = 1570, 2(3), b = 2798, 5(6), c = 2752, 7(6) pm, β = 98, 02(3)°; 5: Space group P1 (No. 2), Z = 2, a = 2115, 5(4), b = 2553, 3(5), c = 3188, 7(6) pm, α = 68, 87(3)°, β = 74, 05(3)°, γ = 69, 70(3)°; 6: Space group P1 (No. 2), Z = 2, a = 1583, 0(3), b = 1709, 6(3), c = 2990, 0(6) pm, α = 80, 41(3)°, β = 88, 86(3)°, γ = 71, 10(3)°).