Bis[μ-1,3-bis(diphenylphosphino)propane]disilver(I) bis(tetrafluoroborate)

Abstract

The dinuclear AgI phosphine complex [Ag2(dppp)2]2+ [dppp = 1,3‐bis­(di­phenyl­phosphino)­propane] has been crystallized as the BF4− salt, viz. [Ag2(C27H26P2)2](BF4)2, in order to reduce the effects of coordination by the anion. The dimeric complex consists of two‐coordinate AgI centers bridged by dppp ligands. The P—Ag—P bond angle deviates significantly from linearity, with a value of 159.66 (3)°. The Ag—P bond distances are close to being equal, with values of 2.3935 (7) and 2.4016 (7) Å. The cation has a center of symmetry midway between the two Ag atoms.

Selective formation of silver(i) bis-phospholane macrocycles and further evidence that gold(i) is smaller than silver(i)

“…The Ag-P bond lengths in [Ag 2 (μ-dppp) 2 ](BF 4 ) 2 (dppp = 1,3-bis(diphenylphosphino)propane; Ag-P: 240.16 (7), 239.35(7) pm) are slightly increased compared to 4-7, while the P-Ag-P bond angles are significantly smaller (P-Ag-P: 159.66(3)°). 6 A P-Ag-P bond angle of 167.3(1)°was observed in [Ag(PPh 3 ) 2 ]BF 4 with small Ag-P bond lengths of 232.1(3) pm and 232.2(3) pm. 23 In 4-7 the large P-Ag-P bond angles result from electronrich bis-phospholane ligands stabilizing the oxidation state +I and the weakly coordinating tetrafluoridoborate anions.…”

“…Figures were drawn with ORTEP. 32 CCDC 1439660 (4), 1439661 (5), 1439662 (6) and 1439663 (7) contain the supplementary crystallographic data for this paper.…”

“…Addition of AgBF 4 to a solution of 3a, 3b, 3c, or 3d 11 in dichloromethane led to macrocycles [Ag 2 (μ-3a-d) 2 ](BF 4 ) 2 (4)(5)(6)(7) in excellent yield by self-assembly under thermodynamic control (Scheme 2).…”

“…Dinuclear silver(I) macrocycles with bridging Ph 2 P(CH 2 ) n PPh 2 ligands are known, for example, with AgNO 3 for n = 3 and 4, 4 AgCl for n = 5, 5 and AgBF 4 with n = 3. 6 Crabtree et al reported the unexpected formation of [Ag 2 {μ-tBu 2 P(CH 2 ) 3 PtBu 2 } 2 ](BF 4 ) 2 as a byproduct when employing AgBF 4 for eliminating chlorido ligands from rhodium complexes. 7 While gold(I) complexes of highly flexible bisphosphines with an even number of carbon atoms in the methylene spacer seem to favor polymerization, 8 the affinity of silver(I) for coordination numbers three and four enables the formation of macrocycles with 1,6-bis(diphenylphosphino) hexane and bridging perchlorate anions as well.…”

catena-Poly[[bis(nitrato-κ2O,O′)copper(II)]-μ-propane-1,3-diylbis(diphenylphosphine oxide)-κ2O:O′]

“…There are examples of 1,1-bis(diphenylphosphino)methane dioxide (dppmO 2 ) acting as both a chelating ligand (Arna  iz et al, 2002) and a bridging ligand (Ding et al, 2000); there are similar examples of 1,2bis(diphenylphosphino)ethane dioxide (dppeO 2 ) chelating (Povey et al, 1991) and bridging between metal centres (Harding et al, 2007;Yang et al, 2000). Although there are many structural examples of 2 P,P H complexes of 1,3-bis(diphenylphosphino)propane (dppp) with transition metals (Davies et al, 2005;Smith et al, 2003;Morgan et al, 2002), and reports of the catalytic ef®cacy of 1,3-bis(diphenylphosphino)propane dioxide (dpppO 2 ) (Ogawa et al, 2004), there are few examples of dpppO 2 complexes of transition metals. One such complex, MoO 2 Cl 2 (dpppO 2 ) (Oh & Mo, 1995), consists of discrete mononuclear units containing a chelating dpppO 2 ligand.…”