Wen-Yann Yeh

[(μ‐H)3Re3(CO)9(η2,η2,η2‐Sc2C2@C3v(8)‐C82)]: Face‐Capping Cluster Complex of an Endohedral Fullerene

Like a miniature trophy, the complex pictured was obtained as the sole product from the reaction of Sc(2)C(2)@C(3v)(8)-C(82) and [(μ-H)(3)Re(3)(CO)(11)(NCMe)] and characterized by IR, visible/near-infrared, and NMR spectroscopy, mass spectrometry, and X-ray diffraction. Coordination of the Re(3) cluster to the unique hexagon oriented perpendicular to the C(3) axis of the fullerene core altered the geometry and electronic properties of Sc(2)C(2)@C(3v)(8)-C(82).

Syntheses, characterization and structures of chromium group carbonyl complexes containing a multifunctional Ph2P(o-C6H4)CHN(CH2)2(o-C6H4N) ligand

Abstract Reactions of the phosphine–imine–pyridine-containing ligand Ph2P(o-C6H4)CHN(CH2)2(o-C6H4N) (PNN) with M(CO)3(NCMe)3 (M=Cr, Mo, W) produce the tridentate complexes fac-M(CO)3(η3-PNN). On the other hand, treating W(CO)4(NCMe)2 with PNN results in the bidentate complex W(CO)4(η2-PNN), which converts to fac-W(CO)3(η3-PNN) upon heating, but no facial→meridional isomerism is evidenced. The new compounds have been characterized by elemental analysis and mass, IR, and NMR spectroscopy. The molecular structures of W(CO)4(η2-PNN), fac-W(CO)3(η3-PNN) and fac-Mo(CO)3(η3-PNN) are determined by an X-ray diffraction study.

Synthesis and reactivity of ditungsten helical complex W2(CO)6(μ-Ph2PCCPPh2)3

Abstract Reaction of W(CO) 3 (Me 3 tach) (Me 3 tach1,3,5-trimethyl-1,3,5-triazacyclohexane) with Ph 2 PCCPPh 2 at room temperature affords a triply-bridged complex W 2 (CO) 6 (μ-Ph 2 PCCPPh 2 ) 3 ( 1 ) and a vinylidene complex W 2 (CO) 6 (μ-Ph 2 PCCPPh 2 )[μ-C 4 H(PPh 2 ) 3 ] ( 2 ). Compound 2 can be obtained by treating 1 with Me 3 tach in dichloromethane. The crystal structures of 1 and 2 are determined by an X-ray diffraction study. The structure of 1 depicts a helical M 2 L 3 framework with an idealized D 3 symmetry. The vinylidene group of 2 is not linear, with the WCC bond angle of 158.6(4)°.

SYNTHESES AND CHARACTERIZATION OF TRICARBONYL TUNGSTEN COMPLEXES CONTAINING 1,1'-BIS(DIPHENYLPHOSPHINO)FERROCENE LIGAND

Abstract Treatment of W(CO) 3 (NCCH 3 ) 3 with 1,1-bis(diphenylphosphino)ferrocene (dppf) affords W(CO) 3 ( NCCH 3 )(η 2 - dppf ) ( 1 ) in 85%) yield. Reaction of 1 with I 2 produces a seven-coordinated complex W(CO) 3 (I) 2 ( η 2 -dppf) ( 2 ), which is further oxidized by H 2 O 2 to give W(CO) 3 (I) 2 ( η 2 -dppf(O)) ( 3 ) in 80% yield. Compound 1 reacts with PMe 3 forming fac -W(CO) 3 ( η 2 -dppf)(PMe 3 ) ( 4 ) in 90% yield. However, reaction of 1 with PPh 2 Cl generates fac -W(CO) 3 ( η 2 -dppf)(PPh 2 H) ( 5 ) and fac -W(CO) 3 ( η 2 -dppf)(PPh 2 OH) ( 6 ) after separation of the reaction mixture by TLC. The structures of compounds 1 and 3 have been characterized by X-ray diffraction methods.

Synthesis and crystal structure of decaphenyltungstenocenium triiodide

Abstract Oxidation of ( η 5 -C 5 Ph 5 ) 2 W ( 1 ) with I 2 affords [( η 5 -C 5 Ph 5 ) 2 W] + I 3 − ( 1 + I 3 − ), which is reconverted to 1 upon treatment with Cp 2 Co. Compound 1 + I 3 − crystallizes in the space group P 2 1 / c with a =14.5258(8), b =18.6515(9) and c =15.5185(8) A; β =111.512(1)°; V =3911.5(4) A 3 ; Z =2; and R 1 / wR 2 =0.050/0.091. The structure of 1 + reveals that the two cyclopentadienyl groups are planar, staggered and exactly parallel.

Tetramerization of alkynes on a tungsten(0) centre to form a cyclopentadienylvinylcarbene complex; crystal structure of [W(CO)(PhCCPh){η5-C3Ph3(C5Ph5)}]

Heating [W(CO)3(MeCN)3] or [W(CO)(PhCCPh)3] with an excess of diphenylacetylene produces [W(CO)(PhCCPh){η5-C3Ph3(C5Ph5)}], which contains a novel Cyclopentadienylvinylcarbene group through coupling of four alkyne ligands on the tungsten(O) centre.

Encapsulation of Formaldehyde and Hydrogen Cyanide in an Open-Cage Fullerene

Reaction of C63 NO2 (Ph)2 (Py) (1) with o-phenylenediamine and pyridine produces a mixture of C63 H4 NO2 (Ph)2 (Py)(N2 C6 H4 ) (2) and H2 O@2. Compound 2 is a new open-cage fullerene containing a 20-membered heterocyclic orifice, which has been fully characterized by NMR spectroscopy, high-resolution mass spectrometry, and X-ray crystallography. The elliptical orifice of 2 spans 7.45 Å along the major axis and 5.62 Å along the minor axis, which is large enough to trap water and small organic molecules. Thus, heating a mixture of 2 and H2 O@2 with hydrogen cyanide and formaldehyde in chlorobenzene affords HCN@2 and H2 CO@2, respectively. The (1) H NMR spectroscopy reveals substantial upfield shifts for the endohedral species (δ=-1.30 to -11.30 ppm), owing to the strong shielding effect of the fullerene cage.

Preparation of Mo, Co and iron group heterometallic clusters linked by cyclotetradeca-1,8-diyne ligand

Thermal reactions of Cp2Mo2(CO)4(m-h 2 -C14H20 )( 1) with Fe3(CO)12 and Ru3(CO)12 produce [Cp2Mo2(CO)4](m,m3-h 2 ,h 2 C14H20)[Fe3(CO)9 ]( 2) and [Cp2Mo2(CO)4](m,m3-h 2 ,h 3 -C14H19)[(m-H)Ru3(CO)9 ]( 3-allyl), respectively, while treatments of 1 with Ru3(CO)10(NCMe)2 and Os3(CO)10(NCMe)2 afford [Cp2Mo2(CO)4](m,m3-h 2 ,h 3 -C14H19)[(m-H)Ru3(CO)9 ]( 3-allenyl) and [Cp2Mo2(CO)4](m,m3-h 2 ,h 2 -C14H20)[Os3(CO)10 ]( 4), respectively. The allene moiety of 3-allenyl rearranges upon heating to give the allyl complex 3-allyl. Compound 1 reacts with Co2(CO)8 to produce [Cp2Mo2(CO)4](m,m-h 2 ,h 2 -C14H20)[Co2(CO)6 ]( 5) and the reaction of Os3(CO)10(m3-h 2 -C14H20) with Co2(CO)8 affords [Os3(CO)10](m3,m-h 2 ,h 2 -C14H20)[Co2(CO)6 ]( 6). The new compounds 2‐6 have been characterized by mass, IR and NMR spectroscopy. The crystal structure of 4 reveals a bridging and a semibridging carbonyl connected to the Os3 cluster.

Phosphine complexes of tungsten(0) poly(alkyne); crystal structures of W(PhCCPh)3(PMe3) and W(TolCCTol)2(η4-C4Tol4)(PMe3)

Abstract Reactions of W(PhCCPh)3L (LCO or NCMe) with PMe3, PPh2Me and PPh3 produce W(PhCCPh)3(PMe3). W(PhCCPh)3−(PPh2Me) and W(PhCCPh)3(PPh3), respectively. Reaction of W(PhCCPh)3(NCMe) with 1,1′-bis(diphenylphosphino)ferrocene (dppf) forms W(PhCCPh)3(η1dppf) and [W(PhCCPh)3]2(η1,η1-dppf). Treating W(RCCR)2(η4-C4R4)(NCMe) (RPh and Tol) with PMe3 affords W(RCCR)2(η4-C4R4)(PMe3) crystallizes in the space group P 3 with a = 14.000(4). c = 11.183(3) A , V = 1898.3(7) A 3 , Z = 2 and R F = 0.032. W(TolCCTol) 2 (η 4 - C 4 Tol 4 ) ( PMe 3 ) crystallizes in the space group P21/c with a = 13.588(2), b = 19.289(5), c = 22.150(5) A , β = 90.57(2)°, V = 5805.(2) A 3 , Z = 4 and R F = 0.055 .

An Open‐Cage Fullerene That Mimics the C60H10 (5,5)‐Carbon Nanotube Endcap to Host Acetylene and Hydrogen Cyanide Molecules

Treatment of the open-cage fullerene C63 H4 NO2 (Ph)2 (Py)(N2 C6 H4 ) (1) with methanol at 150 °C results in an orifice-enlargement reaction to give C69 H8 NO(CO2 Me)(Ph)(Py)(N2 C6 H4 ) (2). The overall yield from C60 to isolated 2 is 6.1 % (four steps). Compound 2 contains a 24-membered elliptic orifice that spans 8.45 Å along the major axis and 6.37 Å along the minor axis. The skeleton of 2 resembles the hypothetic C60 H10 (5,5)-carbon nanotube endcap. The cup-shaped structure of 2 is able to include water, hydrogen cyanide, and acetylene, forming H2 O@2, HCN@2, and C2 H2 @2, respectively. The molecular structures of H2 O@2 and HCN@2 have been determined by X-ray crystallography. The 1 H NMR spectra reveal substantial upfield shifts for the endohedral species, such as δ=-10.30 (for H2 O), -2.74 and -14.26 (for C2 H2 ), and -1.22 ppm (for HCN), owing to the strong shielding effects of the fullerene cage.