Reversible Isomerization via Migration of SnPh3 in S2CPCy3-Bridged Heterobinuclear Compounds. X-ray Structures of [(CO)3Re(μ-S2CPCy3)Mo(SnPh3)(CO)3] and [(CO)3(Ph3Sn)Re(μ-S2CPCy3)Mo(CO)3]
Abstract:The reduction of [(CO)3Re(μ-Br)(μ-S2CPCy3)Mo(CO)3] (1) with Na/Hg and subsequent
reaction of the resulting anionic species with Ph3SnCl yields [(CO)3Re(μ-S2CPCy3)Mo(SnPh3)(CO)3] (2), which, as the temperature increases, partially isomerizes reversibly, through
migration of SnPh3, to [(CO)3(Ph3Sn)Re(μ-S2CPCy3)Mo(CO)3] (3).
“…The Sn−C bond lengths are in the range of 2.18(1)−2.22(1) Å, as found previously in the rhenium complex ( dimethylchlorotin)bis( η 5 - cyclopentadienyl)rhenium, other (triaryltin)rhenium(I) complexes, and other (trimethyltin)metal complexes …”
Section: Resultssupporting
confidence: 82%
“…Except for the Re−C bond length trans to the trihydridostannyl ligand, all Re−C and Re−P bond lengths are shorter than those found in [ReBr(CO) 2 {P(OEt) 3 } 3 ], a rhenium(I) complex with a similar environment. The Re−Sn bond length, 2.7632(6) Å, is similar to those found in (trialkyltin)rhenium(I) complexes and is shorter than the sum of the covalent radii of the metals (∼2.95 Å). 2 ORTEP views of the complex Re(SnH 3 )(CO) 2 [P(OEt) 3 ] 3 ( 6b ) drawn with thermal ellipsoids at the 30% probability level.…”
The trichlorostannyl complexes M(SnCl3)(CO)nP5-n (1−3: M = Mn, Re; P = PPh(OEt)2 (a), P(OEt)3 (b); n = 2, 3) were prepared by allowing chloro MCl(CO)nP5-n compounds to react with an excess of SnCl2·2H2O. Treatment of compounds 1−3 with NaBH4 in ethanol yielded the tin polyhydride derivatives M(SnH3)(CO)nP5-n (4−6). Treatment of 1−3 with MgBrMe gave the trimethylstannyl complexes M(SnMe3)(CO)nP5-n (7−9), and the reaction of 1−3 with MgBr(C≡CH) yielded the trialkynylstannyl derivatives M[Sn(C≡CH)3](CO)nP5-n (10, 11). The alkynylstannyl complexes M[Sn(C≡CR)3](CO)nP5-n (12−14: R = p-tolyl) were also prepared by allowing M(SnCl3)(CO)nP5-n compounds to react with Li+[C≡CR]- in thf. The complexes were characterized by spectroscopy and by X-ray crystal structure determinations of 4a, 6b, and 9b. Reaction of the tin trihydride complexes Re(SnH3)(CO)2P3 (6) with CO2 (1 atm) led to the binuclear OH-bridging bis(formate) derivatives [Re{Sn[OC(H)=O]2(μ-OH)}(CO)2P3]2 (15). A reaction path for the formation of 15, involving the tin hydride bis(formate) intermediate
Re[SnH{OC(H)=O}2](CO)2P3, is discussed. The X-ray crystal structure of 15b is reported
“…The Sn−C bond lengths are in the range of 2.18(1)−2.22(1) Å, as found previously in the rhenium complex ( dimethylchlorotin)bis( η 5 - cyclopentadienyl)rhenium, other (triaryltin)rhenium(I) complexes, and other (trimethyltin)metal complexes …”
Section: Resultssupporting
confidence: 82%
“…Except for the Re−C bond length trans to the trihydridostannyl ligand, all Re−C and Re−P bond lengths are shorter than those found in [ReBr(CO) 2 {P(OEt) 3 } 3 ], a rhenium(I) complex with a similar environment. The Re−Sn bond length, 2.7632(6) Å, is similar to those found in (trialkyltin)rhenium(I) complexes and is shorter than the sum of the covalent radii of the metals (∼2.95 Å). 2 ORTEP views of the complex Re(SnH 3 )(CO) 2 [P(OEt) 3 ] 3 ( 6b ) drawn with thermal ellipsoids at the 30% probability level.…”
The trichlorostannyl complexes M(SnCl3)(CO)nP5-n (1−3: M = Mn, Re; P = PPh(OEt)2 (a), P(OEt)3 (b); n = 2, 3) were prepared by allowing chloro MCl(CO)nP5-n compounds to react with an excess of SnCl2·2H2O. Treatment of compounds 1−3 with NaBH4 in ethanol yielded the tin polyhydride derivatives M(SnH3)(CO)nP5-n (4−6). Treatment of 1−3 with MgBrMe gave the trimethylstannyl complexes M(SnMe3)(CO)nP5-n (7−9), and the reaction of 1−3 with MgBr(C≡CH) yielded the trialkynylstannyl derivatives M[Sn(C≡CH)3](CO)nP5-n (10, 11). The alkynylstannyl complexes M[Sn(C≡CR)3](CO)nP5-n (12−14: R = p-tolyl) were also prepared by allowing M(SnCl3)(CO)nP5-n compounds to react with Li+[C≡CR]- in thf. The complexes were characterized by spectroscopy and by X-ray crystal structure determinations of 4a, 6b, and 9b. Reaction of the tin trihydride complexes Re(SnH3)(CO)2P3 (6) with CO2 (1 atm) led to the binuclear OH-bridging bis(formate) derivatives [Re{Sn[OC(H)=O]2(μ-OH)}(CO)2P3]2 (15). A reaction path for the formation of 15, involving the tin hydride bis(formate) intermediate
Re[SnH{OC(H)=O}2](CO)2P3, is discussed. The X-ray crystal structure of 15b is reported
“…[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 − In those structures, the idealized square-pyramidal geometry is highly distorted and the bridge carbon bears an alkyl or phosphine group. Anions [ II ] − and [ III ] − are related to the metalated polyphosphine structural class, of which there are numerous examples, ,, but this is the first time this unit has been observed as part of an octahedral cluster.…”
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.
“…Using the highly stabilizing bridging ligand η 3 ;η 2 -S 2 CPCy 3 186 led to the isolation of the Re−Mo−Sn chain complex 31a; it was found to be in equilibrium at room temperature with the isomeric Mo−Re−Sn complex 31b (Scheme 11). 187 Reaction of potassium 1,1-dicyanoethylene-2,2-dithiolate with 2 equiv of nitrato(triethylphosphine)gold(I) afforded the trigold chain complex 32 in which each Au−Au bond is bridged by a 1,1-dicyanoethylene-2,2-dithiolato ligand (Chart 16). Its luminescence properties and Raman-determined excited state distortions were investigated.…”
The
chemistry of discrete molecular chains constituted by metals
in low oxidation states, displaying metal–metal proximity and
stabilized by suitable metal-bridging, assembling ligands comprising
at least one soft donor atom is comprehensively reviewed; complexes with a single (hard
or soft) bridging atom (e.g., μ-halide, μ-sulfide,
or μ-PR2
etc.) as well as “closed”
metal arrays (that fall in the realm of cluster chemistry) are excluded.
The focus is on transition metal-based systems, with few excursions
to cases combining transition and post-transition elements. Most relevant
supporting ligands have neutral C, P, O, or S donor (mainly, N-heterocyclic
carbene, phosphine, ether, thioether) or anionic donor (mainly phenyl,
ylide, silyl, phosphide, thiolate) groups. A supporting-ligand-based
classification of the metal chains is introduced, using as the classifying
parameter the number of “bites” (i.e., ligand bridges) subtending each intermetallic separation. The
ligands are further grouped according to the number of donor atoms
interacting with the metal chain (called denticity in the following)
and the column of the Periodic Table to which the set of donor atoms
belongs (in ascending order). A complementary metal-based compilation
of the complexes discussed is also provided in a concise tabular form.
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