Mixed Organometallic–Organic Hybrid Assemblies Based on the Diarsene Complex [Cp₂Mo₂(CO)₄(μ,η²‐As₂)], Ag^I Salts and N‐Donor Organic Molecules

Abstract

The reaction of the organometallic diarsene complex [Cp2Mo2(CO)4(η2‐As2)] (1) with Ag[Al{OC(CF3)3}4] (Ag[TEF]) yielded the AgI monomer [Ag(η2‐1)3][TEF] (2). This compound exhibits dynamic behavior in solution, which allows directed selective synthesis of unprecedented organometallic–organic hybrid assemblies upon its reaction with N‐donor organic molecules by a stepwise pathway, which is supported by DFT calculations. Accordingly, the reaction of 2 with 2,2′‐bipyrimidine (L1) yielded the dicationic molecular compound [{(η2‐1)2Ag}2(μ‐L1)][TEF]2 (3) or the 1D polymer [{(η2‐1)Ag}(μ‐L1)]n[TEF]n (4) depending on the ratio of the reactants. However, its reactions with the pyridine‐based linkers 4,4′‐bipyridine (L2), 1,2‐bis(4‐pyridyl)ethylene (L3) and 1,2‐bis(4‐pyridyl)ethyne (L4) allowed the formation of the 2D polymers [{(η2‐1)Ag}2(μ‐Lx)3]n[TEF]2n [Lx=L2 (5), L3 (6), L4 (7), respectively]. Additionally, this concept was extended to step‐by‐step one‐pot reactions of 1, [Ag(CH3CN)3][Al{OC(CF3)2(CCl3)}4] ([Ag(CH3CN)3][TEFCl]) and linkers L2–L4 to produce the 2D polymers [{(η2‐1)Ag}2(μ,Lx)3]n[TEFCl]2n [Lx=L2 (8), L3 (9), L4 (10), respectively].

Diantimony Complexes [CpR2Mo2(CO)4(μ,η2‐Sb2)] (CpR=C5H5, C5H4tBu) as Unexpected Ligands Stabilizing Silver(I)n (n=1–4) Monomers, Dimers and Chains

“…To rationalize the coordination modes of C towards metal ions and compare them to those in the lighter phosphorus ( A ) and arsenic ( B ) analogs, [9c] Natural Bond Orbital (NBO) calculations were performed for compounds A – C at the B3LYP [28] /def2‐TZVP [29] level of theory. These calculations show that the energy level of the Sb−Sb σ‐bond in C is higher than that of the As−As σ‐bond in B , which is, in turn, higher than that of the P−P σ‐bond in A , showing a clear trend (Figure 1 ).…”

“…[8] To fill this gap, our group developed the concept of using organometallic polyphosphorus (P n ) ( n =2–6) and polyarsenic (As n ) ( n =2–3, 5) ligand complexes as ligands for Ag I and other metal ions. [9] This concept allowed for the synthesis of a novel class of supramolecular assemblies including discrete supramolecular coordination complexes (SCCs) (monomers,[ 9a , 9b ] dimers,[ 9b , 9c , 9e , 10 ] oligomers, [9c] inorganic fullerene‐like nanospheres, [11] nanosized hemispheres [12] and capsules [13] ) as well as 1D, 2D and even 3D coordination polymers (CPs). [ 10a , 14 ] Among the simplest P n and As n compounds are the diphosphorus and diarsenic ligand complexes [Cp 2 Mo 2 (CO) 4 (η 2 ‐E 2 )] (E=P ( A ), [15] As ( B ), [16] Cp=C 5 H 5 ).…”

“…The coordination chemistry of these complexes was thoroughly investigated in the past decade, mainly due to their ease accessibility, relative air stability and adaptive coordination modes. [ 9a , 9c , 9d , 17 ] In contrary, synthesis and supramolecular chemistry studies of higher analogues such as the diantimony complex [Cp 2 Mo 2 (CO) 4 (μ,η 2 ‐Sb 2 )] ( C ) [18] was, until recently, nearly ignored. [19] Roesler et al.…”

Die Diantimonkomplexe [CpR2Mo2(CO)4(μ,η2‐Sb2)] (CpR=C5H5, C5H4tBu) als unerwartete stabilisierende Liganden von Silber(I)n (n=1–4)‐Monomeren, ‐Dimeren und ‐Ketten

“…Um diese Lücke zu schließen, entwickelte unsere Gruppe das Konzept der Verwendung metallorganischer Polyphosphor (P n ) ( n =2–6)‐ und Polyarsen (As n ) ( n =2–3, 5)‐Ligandkomplexe als Liganden für Ag I ‐ und andere Metallionen [9] . Dieses Konzept ermöglichte die Synthese einer neuartigen Klasse von Supramolekülaggregaten, die diskrete supramolekulare Koordinationskomplexe (SCCs) (Monomere, [9a,b] Dimere, [9b,c,e, 10] Oligomere, [9c] anorganische Fulleren‐artigen Nanosphären, [11] nano‐dimensionierte Hemisphären [12] und Kapseln [13] ) sowie 1D‐, 2D‐ und selbst 3D‐Koordinationspolymere (CPs) einschließt [10a, 14] . Zu den einfachsten P n ‐ und As n ‐Verbindungen gehören die Diphosphor‐ und Diarsen‐Ligandkomplexe [Cp 2 Mo 2 (CO) 4 (η 2 ‐E 2 )] (E=P ( A ), [15] As ( B ), [16] Cp=C 5 H 5 ).…”

“…Zu den einfachsten P n ‐ und As n ‐Verbindungen gehören die Diphosphor‐ und Diarsen‐Ligandkomplexe [Cp 2 Mo 2 (CO) 4 (η 2 ‐E 2 )] (E=P ( A ), [15] As ( B ), [16] Cp=C 5 H 5 ). Die Koordinationschemie dieser Komplexe wurde in den letzten zehn Jahren gründlich untersucht, hauptsächlich aufgrund ihrer leichten Zugänglichkeit, ihrer relativen Luftstabilität und ihrer adaptiven Koordinationsformen [9a,c,d, 17] . Im Gegensatz dazu fanden Studien zur Synthese und Supramolekularen Chemie schwererer Analoga wie z.…”