Silver Coordination Chemistry of the Weakly Basic Cage As<sub>4</sub>S<sub>4</sub>

Weis, Philippe; Kratzert, Daniel; Krossing, Ingo

doi:10.1002/ejic.201800430

Cited by 5 publications

(4 citation statements)

References 73 publications

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“…The peak of [AgAs 8 32 S 7 ] + occurred due to small impurities of realgar (As 4 S 4 ) in the used As 4 S 3 . This impurity was also structurally verified during the single crystal structure refinement of 4 and led to the synthesis of two silver complexes of As 4 S 4 that were reported upon recently . All other signals are due to known decomposition reactions of the ligands .…”

Section: Resultssupporting

confidence: 55%

“…This is similar to observations in Raman spectra of Ag[Al(OR F ) 4 ] binding to realgar (As 4 S 4 ) that have shown way stronger fluorescence when the reaction was done in o ‐dfb. This is probably due to decomposition reactions or the generation of small silver particles . Similar to the Raman spectra of 1 , 2 and 3 , the Raman spectrum of 5 shows that coordination to silver lowers the symmetry ligands and therefore some bands of the ligands split and show slightly different vibrational patterns in the silver complex (Figure ).…”

Section: Resultsmentioning

confidence: 61%

“…A previous evaluation of the exchange reactions [Ag(L)] + + L′ → [Ag(L′)] + + L with the weak ligands P 4 , S 8 , P 4 S 3 , P 4 Se 3 , As 4 S 3 and As 4 S 4 as well as a comparison of the calculated HOMO energies of those ligands showed that, in the gaseous state, P 4 Se 3 and As 4 S 3 are comparable to the other ligands . Paired with the experimental evidence that the complexes Ag(L) n [WCA] (L = P 4 , As 4 S 8 , P 4 S 3 , As 4 S 4 ) are accessible, this leads to the conclusion that P 4 Se 3 and As 4 S 3 should be acceptable ligands when combined with a suitable weakly coordinating anion. In the condensed phase, this could be verified with complexes 1 to 5 being accessible complexes of the two cages P 4 Se 3 and As 4 S 3 .…”

Section: Resultsmentioning

confidence: 77%

“…SO 2 tends not to coordinate to silver in 5 , which is surprising considering that the silver complex of the similar cage As 4 S 4 yielded a heteroleptic complex when crystallized from SO 2 Compared to 4 , the ratio of ligand to metal increases from 3:2 to 2:1 when using the weakly coordinating solvent SO 2 instead of o ‐dfb. As in 4 , the As 4 S 3 cages coordinate only via the sulfur atoms.…”

Section: Resultsmentioning

confidence: 99%

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Homoleptic Silver Complexes of the Cages P₄Se₃ and As₄S₃

et al. 2018

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By reacting P 4 Se 3 and As 4 S 3 with Ag[Al(OR F ) 4 ] {-R F = -C(CF 3 ) 3 or -hfip [= -C(H)(CF 3 ) 2 ]} in suitable solvents, (5) were synthesized and characterized by SC-XRD, Mass spectrometry, Raman spectroscopy as well as solution NMR spectroscopy. When using stronger coordinating anions, only P 4 Se 3 forms an isolable complex yielding 1 featuring a [Ag 2 (P 4 Se 3 ) 2 ] 2+ core capped by anions acting as the first example of P 4 Se 3 coordinating through selenium atoms. Upon using the weakly coordinating anion [Al{OC(CF 3 ) 3 } 4 ] -, the dimeric complexes 2 and 4 are accessible in dichloromethane or ortho-difluorobenzene (o-dfb), respectively. Complex 2 shows isolated [Ag 2 (P 4 Se 3 ) 4 - [a] Computational Details: All computations were performed by using the program package TURBOMOLE 7.1. [38] All investigated molecular structures were optimized using the functionals BP86 [39] (with RI approximation [40] ) and together with the basis sets def-SV(P). [41] A fine integration grid (m4) and the default SCF convergence criteria (10 -6 a.u.) were used. The vibrational frequencies of all assessed species were computed with the implemented module AOFORCE [42] and checked for minima (no imaginary frequencies).Preparation of P 4 Se 3 : P 4 Se 3 was obtained by heating stoichiometric amounts of grey selenium and white phosphorus in tetraline followed by extraction and recrystallization in CS 2 , following the literature procedure. [43] FT-Raman: ν = 135 (vw), 214 (m), 317 (sh), 324 (vw), 346 (sh), 365 (vs), 370 (sh), 405 (vw), 484 (w) cm -1 . NMR: 31 P NMR (122 MHz, CS 2 , r.t.): δ = -104.6 [d, 3 P basal , 2 J(P basal , P apical ) = 72 Hz], 37.4 [q, 1 P apical , 2 J(P basal , P apical ) = 72 Hz] ppm. 77 Se (57 MHz, CS 2 , r.t.): δ = 763.3 (m, P 4 77 SeSe 2 ) ppm. 31 P NMR (162 MHz, CD 2 Cl 2 , r.t.): δ = -114.1 [d, 3 P basal , 2 J(P basal , P apical ) = 72 Hz], 30.5 [q, 1 P apical , 2 J(P basal , P apical ) = 72 Hz] ppm. 31 P NMR (162 MHz, SO 2 , r.t.): δ = -113.7 [d, 3 P basal , 2 J(P basal , P apical ) = 72 Hz], 29.6 [q, 1 P apical , 2 J(P basal , P apical ) = 72 Hz] ppm. Mass Spectra: (ASAP, Source Voltage 25 V, Source Offset 25 V, Temperature 400°C, positive): m/z = 173 [P 3 80 Se] + , 365 [HP 4 80 Se 3 ] + .Preparation of As 4 S 3 : As 4 S 3 was obtained by melting stoichiometric amount of the elements for five days at 420°C, followed by Soxhlet-extraction with toluene. FT-Raman: ν = 145 (vw), 172 (w), 186 (m), 207 (m), 217 (m), 230 (sh), 273 (vs), 338 (sh), 359 (m), 375 (vw) cm -1 . Mass Spectra: (ASAP, Source Voltage 25 V, Source Offset 25 V, Temperature 400°C, positive): m/z = 257 [As 3 32 S] + , 289 [As 3 32 S 2 ] + , 321 [As 3 32 S 3 ] + , 396 [As 4 32 S 3 ] + , 397 [HAs 4 32 S 3 ] + , 428 [As 4 32 S 4 ] + , 429 [HAs 4 32 S 4 ] + .

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Section: Resultssupporting

confidence: 55%

Section: Resultsmentioning

confidence: 61%

Section: Resultsmentioning

confidence: 77%

Section: Resultsmentioning

confidence: 99%

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Homoleptic Silver Complexes of the Cages P₄Se₃ and As₄S₃

et al. 2018

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Coordination Chemistry of P₄S₃ and P₄Se₃ towards the Iron Fragments [Fe(Cp)(CO)₂]⁺ and [Fe(Cp)(PPh₃)(CO)]⁺

Weis

Riddlestone

Scherer

et al. 2019

Chemistry A European J

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The complexes Ag(L)n[WCA] (L=P4S3, P4Se3, As4S3, and As4S4; [WCA]=[Al(ORF)4]− and [F{Al(ORF)3}2]−; RF=C(CF3)3; WCA=weakly coordinating anion) were tested for their performance as ligand‐transfer reagents to transfer the poorly soluble nortricyclane cages P4S3, P4Se3, and As4S3 as well as realgar As4S4 to different transition‐metal fragments. As4S4 and As4S3 with the poorest solubility did not yield complexes. However, the more soluble silver‐coordinated P4S3 and P4Se3 cages were transferred to the electron‐poor Fp+ moiety ([CpFe(CO)2]+). Thus, reaction of the silver salt in the presence of the ligand with Fp−Br yielded [Fp−P4S3][Al(ORF)4] (1 a), [Fp−P4S3][F(Al(ORF)3)2] (1 b), and [Fp−P4Se3][Al(ORF)4] (2). Reactions with P4S3 also yielded [FpPPh3−P4S3][Al(ORF)4] (3), a complex with the more electron‐rich monophosphine‐substituted Fp+ analogue [FpPPh3]+ ([CpFe(PPh3)(CO)]+). All complex salts were characterized by single‐crystal XRD, NMR, Raman, and IR spectroscopy. Interestingly, they show characteristic blueshifts of the vibrational modes of the cage, as well as structural contractions of the cages upon coordination to the Fp/FpPPh3 moieties, which oppose the typically observed cage expansions that lead to redshifts in the spectra. Structure, bonding, and thermodynamics were investigated by DFT calculations, which support the observed cage contractions. Its reason is assigned to σ and π donation from the slightly P−P and P−E antibonding P4E3‐cage HOMO (e symmetry) to the metal acceptor fragment.

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