Versatility of Dithiophosphates in the Syntheses of Copper(I) Complexes with Bis(diphenylphosphino)alkanes: Abstraction of Chloride from Dichloromethane

Abstract

Reactions of [Cu(CH(3)CN)(4)]X (X = PF(6), BF(4)) with bis(diphenylphosphino)methane (dppm = Ph(2)PCH(2)PPh(2)) and ammonium dialkyldithiophosphates, (NH(4))[S(2)P(OR)(2)] (R = Et, (i)Pr), yield a series of novel Cu(I) polynuclear complexes, trinuclear [Cu(3)(mu-dppm)(3)(mu(3)-Cl){S(2)P(OEt)(2)}] (PF(6)) 1 and [Cu(3)(mu-dppm)(2){S(2)P(OR)(2)}(2)](PF(6)) (R = Et, 2; (i)Pr, 3), tetranuclear [Cu(4)(mu-dppm)(2) {S(2)P(OEt)(2)}(4)] 4, and hexanuclear [Cu(6)(mu-dppm)(2)(mu(4)-Cl){S(2)P(O(i)()Pr)(2)}(4)](BF(4)) 5. Similarly, the reaction of [Cu(2)(mu-L-L)(2)(CH(3)CN)(2)](PF(6))(2) (L-L, dppm, dppe = Ph(2)PCH(2)CH(2)PPh(2)) with (NH(4))[S(2)P(OR)(2)] yields dinuclear [Cu(2)(mu-dppm)(2){S(2)P(OR)(2)}(2)] 6 (R= (i)Pr, 6A; Et, 6B), trinuclear [Cu(3)(mu-dppe)(3)(mu-Cl)(2){S(2)P(O(i)Pr)(2)}] 9, and polymeric [Cu(mu(2)-dppe){S(2)P(OR)(2)}](n) (R = Et, 7; (i)Pr, 8) complexes. The formation of 1 and 5 involved the abstraction of chloride from dichloromethane when the Cu/S(2)P(OR)(2) ratio exceeded 1, but when ratio was 1:1, no Cl abstraction occurred, as in compound 4. Compound 9, however, was obtained as a 12% byproduct in the synthesis of 8 using a 1:1:1 ratio of Cu/dppe/S(2)P(O(i)Pr)(2). The chloride binds to Cu atoms in a mu(3)-Cl mode by capping one face of the Cu(3) triangle of cluster 1. A mu(4)-Cl caps a single tetragonal face of the trigonal prism of cluster 5, and in the cluster 9, two chlorides bond in mu(2)-Cl modes. Both clusters 2 and 3 exhibit the mu(3)-S mode of bonding for dtp ligands. Only cluster 5 exhibited close Cu...Cu contacts (2.997-3.0238 A). All of compounds were characterized by single-crystal X-ray diffraction and pertinent crystallographic data for 1, 5, and 9 are are follows: (1) C(79)H(76)ClCu(3)F(6)O(2)P(8)S(2), triclinic, P, a = 11.213(1) A, b = 14.142(1) A, c = 25.910(2) A, alpha = 95.328(2) degrees , beta = 99.594(2) degrees , gamma = 102.581(2) degrees , V = 3918.2(6) A(3), Z = 2; (5) C(74)H(100)BClCu(6)F(4)O(8)P(8)S(8), monoclinic, P2(1)/n, a = 25.198(4) A, b = 15.990(3) A, c = 25.421(4) A, beta = 106.027(3) degrees , V = 9845(3)A(3), Z = 4; (9) C(84)H(86)Cl(2)Cu(3)O(2)P(7)S(2), monoclinic, C2/c, with a = 24.965(3) A, b = 17.058(2) A, c = 20.253(2) A, beta = 95.351(4) degrees , V = 8587.4(17)A(3), Z = 4.

Polymeric Organometallic Architectures of Novel PSe Anions

“…Current synthetic efforts in the field concentrate on metal complexes with ligands designed by formally replacing O atoms in phosphate ions with OR, SR, S, Se, OSe and combinations thereof, and ultimately on the construction of larger molecular aggregates. [15][16][17][18][19][20] In previous work, it was shown that reactions of metal salts MX (X = alkoxide, thiolate, carboxylate) with Lawessons reagent (L.R.) [{RP(S)A C H T U N G T R E N N U N G (m-S)} 2 ] (R = 4-anisyl) [21] or the analogous Se compound Woollins reagent (W.R.) [{PhP(Se)A C H T U N G T R E N N U N G (m-Se)} 2 ] [8,22] offer an alternative route to complexes containing P/S-or P/Se-based anionic ligands.…”

Copper(I) complexes of new N2S2 donor Schiff-base ligands derived from 1,2-bis-(2-amino-phenylsulfanyl)ethane

“…The main objective is to produce new functional materials with specific molecular arrangements capable of showing the desirable properties [16,17]. With flexible ligands, the competition between chelating and bridging coordination modes is an important factor in producing mono, di, and polynuclear metal complexes [18][19][20][21]. We have recently studied the coordination behavior of several Schiff-base ligands such as ca 2 en, Phca 2 en, Phca 2 dab, ca 2 dapte and (thio) 2 dapte [22][23][24][25][26][27].…”

The influence of alkane spacer of bis(diphenylphosphino)alkanes on the nuclearity of silver(I): Syntheses and structures of P,P′-bridged clusters and coordination polymers involving dithiophosphates

“…The increase in chain length of diphosphine from -(CH 2 ) 2 -in dppe to -(CH 2 ) 4 -in dppb, produces two types of polymers depending on the molar ratio used; a zigzag chain, 7 (Fig. 5), in which dppb bridges two Ag(dtp) units having a similar bonding pattern that observed in dppe polymer 5a, 5a 0 and [Cu(dppe){S 2 P(OR) 2 }] 1 [30], and the other zigzag chain 8 in which the dppb ligands bridge dimeric Ag 2 (dtp) 2 units (Fig. 6).…”

“…Calc. for C 30 The method is the same as for 1, except using dichloromethane as solvent with [Ag 2 (dppb) 2 …”