Discrete and polymeric organometallic‐organic hybrid materials based on the diphosphorus complex [Cp₂Mo₂(CO)₄(η²‐P₂)], Cu salts, and 2,2′‐bipyrimidine

The reaction of the diphosphorus complex [Cp2Mo2(CO)(4)((2)-P-2)] (1), with the Cu-I salts [Cu(CH3CN)(4)][BF4] or [Cu(CH3CN)(4)][PF6], and a mixture of [Cu(CH3CN)(4)][BF4] and CuCl in the presence of 2,2-bipyrimidine (2) is studied. Depending on the Cu-I salts used and the layering solvent involved in the crystallisation, a variety of novel coordination compounds are accessible in moderate to excellent yields (26-80%): the novel dicationic molecular organometallic-organic hybrid complexes [{Cp2Mo2(CO)(4)(mu(3),(1:2:2)-P-2)}(4)(mu(2),(1:1:1:1)-C8H6N4)Cu-2][BF4](2) (3) and [{Cp2Mo2(CO)(4)(mu(3),(1:2:2)-P-2)}(2){Cp2Mo2(CO)(4)(mu(3),(2:2:2)-P-2)}(2)(mu(2),(1:1:1:1)-C8H6N4)Cu-2][PF6](2) (4), the unique neutral 1D organometallic-organic hybrid polymer [{Cp2Mo2(CO)(4)(mu(4),(1:1:2:2)-P-2)}(2)(mu(2),(1:1:1:1)-C8N6N4)(CuCl)(2)](n) (5) and the unprecedented 2D organometallic-organic hybrid polymer [{Cp2Mo2(CO)(4)(mu(4),(1:1:2:2)-P-2)}(mu(2),(1:1:1:1)-C8H6N4){Cu-2(mu-Cl)}](2)[BF4](2n) (6)

Highly soluble Cu(I)-acetonitrile salts as building blocks for novel phosphorus-rich organometallic-inorganic compounds

The synthesis of the air-stable and highly soluble Cu(I)-acetonitrile salts [Cu(CH3CN)3.5][FAl] (1) ([FAL] = FAl{OC(C6F10)(C6F5)}3) and [Cu(CH3CN)4][TEF] (2) ([TEF] = Al{OC(CF3)3}4) is presented. Compound 1 reacts with the organometallic polyphosphorus complexes [Cp2Mo2(CO)4(ƞ2-P2)] (A) and [(Cp*Fe(ƞ5-P5)] (B) and salt 2 reacts with B to form one new (3) and three unprecedented (4-6) phosphorus-rich Cu(I) dimers with the general formulas [Cu2(µ,ƞ1:ƞ1-A)2(ƞ2-A)2][FAl]2 (3), [Cu2(µ,ƞ1:ƞ1-A)2(ƞ1-CH3CN)4][FAl]2 (4), [Cu2(µ,ƞ1:ƞ1-B)2(ƞ1-CH3CN)4][FAl]2 (5) and [Cu2(µ,ƞ1:ƞ1-B)2(ƞ1-CH3CN)4][TEF]2 (6)

The Diphosphorus Complex [Cp₂Cr₂(CO)₄(η²‐P₂)] as a Building Block in the Coordination Chemistry of Silver

The reaction of the tetrahedral diphosphorus complex [Cp2Cr2(CO)(4)(eta(2)-P-2)] (Cp = C5H5) (2) with Ag[Al{OC(CF3)(3)}(4)] (AgTEF) (3) leads to the formation of the Ag-I dimer [Ag-2(eta(2)-2) (eta(1)-2)(eta(1):eta(1)-2)(2)][TEF](2) (5). This dimer can be used as a suitable precursor for the synthesis of the unprecedented 1D organometallic-organic hybrid polymer [Ag-2(eta(1)-2)(2)(mu,eta(1):eta(1)-2)(2){mu,eta(1):eta(1)-(C8H4N2)}](n)[TEF](2n) (8) upon its reaction with 1,4-dicyanobenzene (7). The driving force for this supramolecular assembly reaction is supported by DFT calculation

Tuning the dimensionality of organometallic-organic hybrid polymers assembled from [Cp₂Mo₂(CO)₄(η²-P₂)], rigid bipyridyl linkers and Ag ions

The reactions of the P₂ ligand complex [Cp₂Mo₂(CO)₄(η²-P₂)] (Cp = C₅H₅, 1) with Ag[Al{OC(CF₃)₃}₄] (Ag[TEF]) in the presence of the rigid bipyridyl linkers 1,2-di(pyridin-4-yl)ethyne (3), 4,4′-bis(pyridin-4-ylethynyl)-1,1′-biphenyl (4) and 4,4′-bipyridine (5) possessing various lengths are studied. The reaction with the longer linkers (3 and 4) leads to the formation of the 1D organometallic–organic hybrid polymers [{Cp₂Mo₂(CO)₄(μ₄,η¹˸¹˸²˸²-P₂)}₂{Cp₂Mo₂(CO)₄(μ₃,η¹˸²˸²-P₂)}₂(μ,η¹˸¹-C₁₂H₈N₂)Ag₂]n[TEF]₂n (6) and [{Cp₂Mo₂(CO)₄(μ₄,η¹˸¹˸²˸²-P₂)}₂{Cp₂Mo₂(CO)₄(μ₃,η¹˸²˸²-P₂)}₂(μ,η¹˸¹-C₂₆H₁₆N₂)Ag₂]n[TEF]₂n (7) in high selectivity. A similar reaction with the short linker 5 affords a mixture of the 2D hybrid polymers [{Cp₂Mo₂(CO)₄(μ₄,η¹˸²˸²˸²-P₂)}₂(μ,η¹˸¹-C₁₃H₁₄N₂)Ag₂]n[TEF]₂n (8) and the 3D hybrid network [{Cp₂Mo₂(CO)₄(μ₄,η¹˸¹˸²:²-P₂)}₂(μ,η¹˸¹-C10H8N₂)Ag]n[TEF]₂n (9). However, a selective synthesis of 8 or 9 is possible when the reaction is performed at 0 °C and 60 °C, respectively