μ₄-Dicarbyne complex with a dimetallacyclobutatriene core: A new binding mode of C₂species

Abstract

Reaction of a permetallated ethene, (mu4-C=C)Fe2R-mu2Cp*2(CO)10, with diphenylacetylene affords the adduct with a new C2-binding mode, a mu4-dicarbyne complex, (mu4-C-C)Fe2Ru2Cp*2(CO)6(mu-Ph-C[triple bond]C-Ph), containing a dimetallacyclobutariene core.

Synthesis and Structure of Cationic Triruthenium Complexes Containing an Oxametallacycle: Reversible Carbon−Oxygen Bond Formation and Scission on an Electron-Deficient Triruthenium Plane

“…Relevant bond lengths and angles of 8 are listed in Table . Although there have been a few examples containing a μ- or a μ 3 -2-oxametallacyclopentenyl ligand, it is noteworthy that the 2-oxaruthenacyclopentyl skeleton in 8 was a very rare example of C−O bond formation by reductive coupling between the μ 3 -diruthenaallyl moiety and the μ-hydroxo group. Formation of 8 represents a novel method to introduce a functional group into a hydrocarbyl ligand using a cationic cluster.…”

C−C Coupling of a Permetalated Ethene, (μ4-CC)Ru2(FeCp*)2(CO)10, with Alkynes, and Isolation of a Labile MeCN Adduct, (μ4-CC)Ru2(FeCp*)2(CO)8(NCMe)2

“…In particular, interaction with Ru 3 (CO) 12 resulted in sequential formation of tetranuclear ( 2 ) and octanuclear cluster compounds ( 3 ), which were characterized as the unique permetalated ethene and ethane species, respectively (Scheme ),and, for 2 with a reactive CC group, we further studied its reactivity. In previous papers, we reported for 2 (1) formal, stepwise hydrogenation of the C 2 ligandand (2) conversion into a unique μ 4 -dicarbyne (ethandiylidyne) complex with a dimetallacyclobutatriene core ( 4 ) . In this note we report some derivative chemistry of 2 and 4 .…”

Flexible Platinum(0) Coordination to a Ditungsten Ethanediylidyne

“…The few known tetra‐metalated dicarbido assemblies all adhere to ethyn‐di‐yl or ethen‐tetra‐yl bonding descriptions that retain a degree of C−C multiple bonding. The exception, [Fe 2 Ru 2 (μ 4 ‐C 2 )(CO) 8 (μ‐PhCCPh)(Cp*) 2 ] may be described as involving Ru=C and Ru=Ru multiple bonding within a Ru 2 C 2 trapezoidal dimetallacyclobutatriene with minimal C−C double bond character ( r C–C =1.313 Å). The crystallographically centrosymmetric molecular structure of 8 in 8 ⋅CH 2 Cl 2 has the two dimetallacyclopropene units coplanar such that some conjugation between the WAuC rings is plausible but not reflected in the long C1−C1′ bond length (1.398(16) Å).…”

“…. [17] Selected bond lengths []and angles [8 8]: C1-C1' 1.398- (16), C1-W 1.912(9), C1-Au 2.070(9);C 1 '-C1-W 152.7(10), C1'-C1-Au 118.9(9). Figure 4.…”

“…[13] Ther esulting orange product, [W 2 (m-C 2 Au 2 Cl 2 )(CO) 4 (Tp*) 2 ]( 8), contains two AuCl fragments transversely added across both WCb onds and, being much more soluble than 7,i sm ore amenable to complete spectral and structural characterization ( Figure 3a nd the Supporting Information). Thef ew known tetra-metalated dicarbido assemblies all adhere to ethyn-di-yl [14] or ethen-tetra-yl [15] bonding descriptions that retain ad egree of CÀCm ultiple bonding.T he exception, [Fe 2 Ru 2 (m 4 -C 2 )(CO) 8 (m-PhCCPh)-(Cp*) 2 ] [16] may be described as involving Ru=Ca nd Ru=Ru Figure 2. Molecular structure of 4 in acrystal of 4•CH 2 Cl 2 (ellipsoids set at 50 %p robability,h ydrogen atoms and solvent omitted,p yrazolyl rings simplified).…”