Cluster Growth Reactions with Selenido‐Carbonyl Clusters − Synthesis, Characterisation and Theoretical Study of the Dimetallic closo Clusters [WRu₃(μ₄‐Se)₂(μ‐CO)₄(CO)₆(L)₂] (L = Phosphane) and of the Donor‐Acceptor Adduct [(CO)₅W(μ₄‐Se)Ru₃(μ₃‐Se)(CO)₇{P(CH₂Ph)Ph₂}₂]

Abstract

The open-triangular, nido clusters of the type [Ru 3

Chalcogen-capped ruthenium carbonyl clusters derived from diphosphazane mono- and dichalcogenides of the type X2P(E)N(R)PX2 and X2P(E)N(R)P(E)X2 (E=S or Se)

“…The reaction of the cluster [Ru 3 ( 3 -S)(l sb -CO)-(CO) 7 {j 2 -P,P-Ph 2 PN((S)-* CHMePh)PPh 2 }] (A) with (PhO) 2 PN(Me)P(S)(OPh) 2 (L 6 ) in boiling toluene in the presence of Me 3 NO as decarbonylating agent gave a mixture of products which could not be separated and isolated in a pure state. However, based on 31 P-31 P COSY spectrum and observed 31 P chemical shifts (see Section 2), one of the products is tentatively identified as [Ru 3 (l 3 -S) 2 (CO) 5 agent also gave a mixture of products which could not be separated and isolated in a pure form. Based on IR and NMR spectroscopic data (see Section 2), one of the products can be tentatively identified as [Ru 3 (l 3 -S) 2 (CO) 5 …”

“…However, based on 31 P-31 P COSY spectrum and observed 31 P chemical shifts (see Section 2), one of the products is tentatively identified as [Ru 3 (l 3 -S) 2 (CO) 5 agent also gave a mixture of products which could not be separated and isolated in a pure form. Based on IR and NMR spectroscopic data (see Section 2), one of the products can be tentatively identified as [Ru 3 (l 3 -S) 2 (CO) 5 …”

“…Extensive studies have also been reported on a variety of chalcogen bridged carbonyl clusters bearing diphosphines of the type (Ph 2 P) 2 R (R = C " C, E = Se, M = Ru [8d]; R = CH 2 , E = S, M = Os [9a]; R = CH 2 , E = Se, M = Fe [13a], Ru [8e,13b,13c], Os [9b]; R = CH 2 , E = Te, M = Ru [8b]; R = (CH 2 ) 2 , E = Se, M = Fe [13a], Ru [8e,13d]; R = (CH 2 ) 3 , E = Se, M = Ru [8c]; R = (C 5 H 4 ) 2 Fe, E = Se, M = Fe [13a], Ru [13d,13e]; R = C 6 H 4 {(CH 2 ) 2 -1,2)}, E = S, M = Ru [11]; R = C 6 H 4 (CH 2 ) 2 -1,2), E = Se, M = Fe, Ru [14]; R = C 5 H 2 O 2 , E = S, M = Ru [15]). Chalcogen bridged heterometallic clusters bearing both mono-and diphosphines have been reported recently by Predieri [5] and Braunstein [16]. On the other hand, there are only two reports [17] on the analogous chalcogen bridged clusters bearing diphosphazanes as ancillary ligands.…”

“…Furthermore, these clusters have the ability to add or remove ligands or electrons while still retaining their integrity. Such chalcogen bridged clusters can be regarded as models for extended inorganic solids [4] and have been utilized for cluster growth reactions [5] and synthesis of heterometallic clusters [6]. Chalcogen bridged clusters bearing phosphorus ligands are synthesized by one of the following routes: (1) treatment of a zero-valent metal carbonyl of the type M 3 (CO) 12 (M = Fe, Ru, Os) with a phosphine chalcogenide R 3 P(E) (E = S, Se) in the presence of Me 3 NO as a decarbonylating agent [7], (2) reaction of a chalcogen-bridged cluster with a phosphine [8], (3) reaction of a phosphine substituted cluster with H 2 S [9a] and (4) reaction of phosphine substituted hydrido cluster with elemental chalcogen [9b].…”

“…Chalcogen(E) bridged carbonyl clusters bearing monophosphines of the type PR 3 (R = Ph [7,8b,8e, 10], p-tolyl [10a], C 6 H 4 [10b] or C 6 H 2 {(OMe) 3 -2,4,6} [11]) and PR 2 R 0 (R = Me, R 0 = Ph [8a]; R = Ph, R 0 = benzyl [10b], Me [5], OMe [5], 2-thienyl [12a], (2-pyridyl)-2-thienyl [12b] or 2-pyridyl [12c]) have been investigated to obtain both tri-and tetranuclear clusters of different structural types. Extensive studies have also been reported on a variety of chalcogen bridged carbonyl clusters bearing diphosphines of the type (Ph 2 P) 2 R (R = C " C, E = Se, M = Ru [8d]; R = CH 2 , E = S, M = Os [9a]; R = CH 2 , E = Se, M = Fe [13a], Ru [8e,13b,13c], Os [9b]; R = CH 2 , E = Te, M = Ru [8b]; R = (CH 2 ) 2 , E = Se, M = Fe [13a], Ru [8e,13d]; R = (CH 2 ) 3 , E = Se, M = Ru [8c]; R = (C 5 H 4 ) 2 Fe, E = Se, M = Fe [13a], Ru [13d,13e]; R = C 6 H 4 {(CH 2 ) 2 -1,2)}, E = S, M = Ru [11]; R = C 6 H 4 (CH 2 ) 2 -1,2), E = Se, M = Fe, Ru [14]; R = C 5 H 2 O 2 , E = S, M = Ru [15]).…”