Abstract
The compound bis-{μ3-2,5-bis-[N-(4-iso-propyl-phen-yl)-P,P-di-phenyl-phospho-r-im-i-do-yl]pyrrol-1-ido-κ3 N:N':N''}tris-ilver(I) tri-fluoro-methane-sulfonate deuterated benzene penta-solvate, [Ag3(C46H44N3P2)2](CF3O3S)·5C6D6, (I), was synthesized from two equivalents of NaL [L = 2,5-(4- i PrC6H4N=PPh2)C4H2N] and three equivalents of AgOTf (OTf = OSO2CF3). High-quality crystals of (I) formed with five deuterated benzene solvent mol-ecules in the asymmetric unit. Notably, the bond lengths and angles between the three silver atoms are markedly different, unlike in most other reported tris-ilver complexes that tend to form three equivalent metal centers. Additionally, to the best of our knowledge, this is the first report of a tris-ilver complex with six nitro-gen donors from two bis-phosphinimine ligands.
Highlights
The compound bis{3-2,5-bis[N-(4-isopropylphenyl)-P,P-diphenylphosphorimidoyl]pyrrol-1-ido-3N:N0:N00}trisilver(I) trifluoromethanesulfonate deuterated benzene pentasolvate, [Ag3(C46H44N3P2)2](CF3O3S)Á5C6D6, (I), was synthesized from two equivalents of NaL [L = 2,5-(4-iPrC6H4N PPh2)C4H2N] and three equivalents of AgOTf (OTf = OSO2CF3)
Tang and Zhao recently demonstrated that a trisilver cluster was highly favoured with six nitrogen donors, even when ten equivalents of silver triflate were used (Tang & Zhao, 2020)
There have been a few examples of silver complexes supported by phosphinimine ligands [Cambridge Structural Database, Version 5.41, update of December 2020; Groom et al, 2016; CSD refcodes OHILEZ and OHILUP (Aguirre Quintana et al, 2020), LAHCII (Brown et al, 2010), UKEGUO (Thirumoorthi et al, 2016) AVAPEV and AVAPIZ (Jha et al, 2021)], we are not aware of any trisilver complexes with bisphosphinimine ligands, as is the case with the structure reported
Summary
Silver clusters have been reported extensively in the literature, and trisilver clusters tend to be common. As a result of the silver atoms being coordinated to different nitrogen atoms, the Ag1—Ag3 and Ag1—Ag2 distances are substantially longer than Ag2— Ag3, which in turn causes an acute Ag2—Ag1—Ag3 angle of 52.186 (5), far less than the average value of 60.0 (2) found in the CSD. Throughout the aforementioned examples we are not aware of any complexes that have such a significant difference in bond lengths when comparing all three silver distances. Johnson et al (2009) reported a trisilver complex Ag3L3 {L = 2-1,3-bis[2,6-(diisopropylphenyl)triazenide]} and described their complex as a silver triangle possessing equilateral geometry such that their Ag—Ag bond distances are approximately the same within error (CSD refcode OGOHIC). The current complex (I) shows a distorted linear geometry when only considering Ag—N contacts with N—Ag—N angles averaging 172.8 (2) (Table 1)
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