“…The isotopic distribution of the envelope surrounding the m / z 951 molecular ion matches that calculated for the formula of 1 . The IR absorptions in the carbonyl region of 1 (Figure a) show a pattern similar to that recorded for Ru 3 (CO) 9 (μ 3 -NPh)(μ 3 -S), whereas the triosmium analogue Os 3 (CO) 9 (μ 3 -NSiMe 3 )(μ 3 -S) was found to display a simpler pattern, with only five absorption peaks ranging from 2065 to 1978 cm -1 1 IR spectra in the carbonyl region of (a) Os 3 (CO) 9 (μ 3 -NPh)(μ 3 -S) ( 1 ), (b) Os 3 (CO) 9 (μ 3 -η 2 -(PhN) 2 SO)(μ 3 -S) ( 2 ), and (c) Os 3 (CO) 8 (NCMe)(μ 3 -NPh)(μ 3 -S) ( 3 ). 1 …”
Section: Resultssupporting
confidence: 62%
“…In contrast, the variable-temperature 13 C NMR study for the analogous complex Os 3 (CO) 9 (μ 3 -NSiMe 3 )(μ 3 -S) consisted of a slow-exchange spectrum at −40 °C with the carbonyl carbon resonances in a 1:2:2:2:2 pattern, which equilibrated to give a single resonance at ca. 70 °C . A reversible closing/opening process of the Os−Os bonds was proposed.…”
Section: Resultsmentioning
confidence: 98%
“…Treatment of Os 3 (CO) 12 with PhNSO in refluxing methylcyclohexane produces Os 3 (CO) 9 (μ 3 -NPh)(μ 3 -S) ( 1 ) in 72% yield (eq 1). A related complex Os 3 (CO) 9 (μ 3 -NSiMe 3 )(μ 3 -S) was previously prepared from the thermal reaction of Os 3 (CO) 12 and Me 3 SiNSNSiMe 3 …”
Section: Resultsmentioning
confidence: 99%
“…This complex consists of an open triangular cluster of three Os(CO) 3 units with triply-bridging phenylimido and sulfido groups on opposite sites of the Os 3 triangle. Compound 1 is structurally similar to Os 3 (CO) 9 (μ 3 -NSiMe 3 )(μ 3 -S), Ru 3 (CO) 9 (μ 3 -NPh)(μ 3 -S), Fe 3 (CO) 9 (μ 3 -NTol)(μ 3 -S), M 3 (CO) 9 (μ 3 -NPh) 2 (M = Fe, Ru 19 ), and M 3 (CO) 9 (μ 3 -S) 2 (M = Fe, Ru, Os 22 ), which contain 50 cluster valence electrons and require only two metal−metal bonds to satisfy the 18-electron rule on each metal atom. 3 ORTEP diagram of Os 3 (CO) 9 (μ 3 -NPh)(μ 3 -S) ( 1 ).…”
Reaction of Os(3)(CO)(12) with thionylaniline (PhN=S=O) in refluxing methylcyclohexane produces Os(3)(CO)(9)(&mgr;(3)-NPh)(&mgr;(3)-S) (1) in good yield. When Os(3)(CO)(10)(NCMe)(2) is treated with PhN=S=O at room temperature, compound 1 and Os(3)(CO)(9)(&mgr;(3)-eta(2)-(PhN)(2)SO)(&mgr;(3)-S) (2) result. Compound 1 reacts with trimethylamine oxide in the presence of acetonitrile to give Os(3)(CO)(8)(NCMe)(&mgr;(3)-NPh)(&mgr;(3)-S) (3). Compounds 1-3 were characterized by mass, IR, and NMR spectroscopies, and their structures were determined by single-crystal X-ray diffraction. Crystal data for 1: monoclinic (C2/c), a = 16.603(7) Å, b = 8.679(4) Å, c = 29.009(6) Å, beta = 102.08(2) degrees, Z = 8, R (R(w)) = 0.036 (0.039). Crystal data for 2: triclinic (P&onemacr;), a = 9.723(4) Å, b = 15.704(4) Å, c = 18.455(7) Å, alpha = 113.17(3) degrees, beta = 102.48(3) degrees, gamma = 89.97(3) degrees, Z = 4, R (R(w)) = 0.030 (0.026). Crystal data for 3: monoclinic (P2(1)/n), a = 18.792(3) Å, b = 8.856(3) Å, c = 26.210(9) Å, beta = 93.72(2) degrees, Z = 8, R (R(w)) = 0.066 (0.063).
“…The isotopic distribution of the envelope surrounding the m / z 951 molecular ion matches that calculated for the formula of 1 . The IR absorptions in the carbonyl region of 1 (Figure a) show a pattern similar to that recorded for Ru 3 (CO) 9 (μ 3 -NPh)(μ 3 -S), whereas the triosmium analogue Os 3 (CO) 9 (μ 3 -NSiMe 3 )(μ 3 -S) was found to display a simpler pattern, with only five absorption peaks ranging from 2065 to 1978 cm -1 1 IR spectra in the carbonyl region of (a) Os 3 (CO) 9 (μ 3 -NPh)(μ 3 -S) ( 1 ), (b) Os 3 (CO) 9 (μ 3 -η 2 -(PhN) 2 SO)(μ 3 -S) ( 2 ), and (c) Os 3 (CO) 8 (NCMe)(μ 3 -NPh)(μ 3 -S) ( 3 ). 1 …”
Section: Resultssupporting
confidence: 62%
“…In contrast, the variable-temperature 13 C NMR study for the analogous complex Os 3 (CO) 9 (μ 3 -NSiMe 3 )(μ 3 -S) consisted of a slow-exchange spectrum at −40 °C with the carbonyl carbon resonances in a 1:2:2:2:2 pattern, which equilibrated to give a single resonance at ca. 70 °C . A reversible closing/opening process of the Os−Os bonds was proposed.…”
Section: Resultsmentioning
confidence: 98%
“…Treatment of Os 3 (CO) 12 with PhNSO in refluxing methylcyclohexane produces Os 3 (CO) 9 (μ 3 -NPh)(μ 3 -S) ( 1 ) in 72% yield (eq 1). A related complex Os 3 (CO) 9 (μ 3 -NSiMe 3 )(μ 3 -S) was previously prepared from the thermal reaction of Os 3 (CO) 12 and Me 3 SiNSNSiMe 3 …”
Section: Resultsmentioning
confidence: 99%
“…This complex consists of an open triangular cluster of three Os(CO) 3 units with triply-bridging phenylimido and sulfido groups on opposite sites of the Os 3 triangle. Compound 1 is structurally similar to Os 3 (CO) 9 (μ 3 -NSiMe 3 )(μ 3 -S), Ru 3 (CO) 9 (μ 3 -NPh)(μ 3 -S), Fe 3 (CO) 9 (μ 3 -NTol)(μ 3 -S), M 3 (CO) 9 (μ 3 -NPh) 2 (M = Fe, Ru 19 ), and M 3 (CO) 9 (μ 3 -S) 2 (M = Fe, Ru, Os 22 ), which contain 50 cluster valence electrons and require only two metal−metal bonds to satisfy the 18-electron rule on each metal atom. 3 ORTEP diagram of Os 3 (CO) 9 (μ 3 -NPh)(μ 3 -S) ( 1 ).…”
Reaction of Os(3)(CO)(12) with thionylaniline (PhN=S=O) in refluxing methylcyclohexane produces Os(3)(CO)(9)(&mgr;(3)-NPh)(&mgr;(3)-S) (1) in good yield. When Os(3)(CO)(10)(NCMe)(2) is treated with PhN=S=O at room temperature, compound 1 and Os(3)(CO)(9)(&mgr;(3)-eta(2)-(PhN)(2)SO)(&mgr;(3)-S) (2) result. Compound 1 reacts with trimethylamine oxide in the presence of acetonitrile to give Os(3)(CO)(8)(NCMe)(&mgr;(3)-NPh)(&mgr;(3)-S) (3). Compounds 1-3 were characterized by mass, IR, and NMR spectroscopies, and their structures were determined by single-crystal X-ray diffraction. Crystal data for 1: monoclinic (C2/c), a = 16.603(7) Å, b = 8.679(4) Å, c = 29.009(6) Å, beta = 102.08(2) degrees, Z = 8, R (R(w)) = 0.036 (0.039). Crystal data for 2: triclinic (P&onemacr;), a = 9.723(4) Å, b = 15.704(4) Å, c = 18.455(7) Å, alpha = 113.17(3) degrees, beta = 102.48(3) degrees, gamma = 89.97(3) degrees, Z = 4, R (R(w)) = 0.030 (0.026). Crystal data for 3: monoclinic (P2(1)/n), a = 18.792(3) Å, b = 8.856(3) Å, c = 26.210(9) Å, beta = 93.72(2) degrees, Z = 8, R (R(w)) = 0.066 (0.063).
“…The related M 3 E 2 nido- octahedral compounds have been known for some time, − and the compounds reported here may be viewed as an isolobal replacement of Fe(CO) 3 – by P or As. [Et 4 N][ II ] and [Et 4 N][ III ] are electron precise, and the core electron count of each is consistent with that predicted by the Wade–Mingos rules for a nido- octahedron with seven skeletal electron pairs distributed across five vertices …”
A series of clusters of the form [Et4N][Fe2(CO)6(μ3-As)}(μ3-EFe(CO)4)], where E is either P or As, were synthesized from [Et4N]2[HAs{Fe(CO)4}3] and ECl3. AsCl3 gives the As-only compound; PCl3 produces compounds having two As atoms with one P atom, or one As atom and two P atoms, and they can exist as two possible isomers, one of which is chiral. The As2P and AsP2 clusters cocrystallize, and their structure as determined by single-crystal X-ray diffraction is given along with the structure of the As-only cluster. Analytical data as well as density functional theory calculations support the formation and geometries of the new molecules.
Die Chemie der Carbonylmetallcluster ist kompliziert und eben erst in Ansatzen verstanden; daher bemuht man sich gegenwartig vor allem um ein Verstandnis der Reaktivitat dieser Verbindungen. In dieser Ubersicht werden Synthesen und Reaktionen von Clustern beschrieben, in denen die Carbonylmetallfragmente durch Hauptgruppenelemente verbriickt sind. Warum sollte man Cluster durch den Einbau eines Hauptgruppenelements noch komplizierter machen, als sie ohnehin sind? Am Beispiel p3-verbriickter Carbonylmetallcluster wird gezeigt, daO das Hauptgruppenelement eine fur die Analyse von Reaktionswegen wichtige Funktion erfullt: Es halt die Carbonylmetallfragmente auch dann zusammen, wenn die Bindung zwischen ihnen im Verlauf einer Reaktion gebrochen wird. Dreikernige, p3-verbriickte Cluster erweisen sich als klein genug, um die Einzelschritte clustertypischer Reaktionen wie etwa der reversiblen affnung von Metall-Metall-Bindungen aufklaren zu konnen. Zugleich sind sie groB genug, um durch ihre vielfiiltige Reaktivitat zu uberraschen. DaR man durch genaue Studien an dreikernigen, RX-verbriickten (X = N, P, As, Sb, Bi) Carbonylmetallclustern, einem sehr kleinen Ausschnitt der Carbonylmetallcluster-Chemie, allgemeine Reaktionsprinzipien dieser Chemie verstehen lernen kann, sol1 gezeigt werden.
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