Theoretical study of thermal rearrangements of α‐silylalcohols: Effects of substituents attached to the silicon atom on the reactions

To investigate the effects of substituents attached to the silicon atom on the thermal rearrangement reactions of α‐silyl alcohols, the thermal rearrangement reactions of dimethylsilyl methanol (CH₃)₂SiHCH₂OH and vinylsilyl methanol CH₂?CHSiH₂CH₂OH were studied by ab initio calculations at the G3 level. Geometries of various stationary points were fully optimized at the MP2(full)/6‐31G(d) and MP2(full)/6‐311G(d,p) levels, and harmonic vibrational frequencies were calculated at the same levels. The reaction paths were investigated and confirmed by intrinsic reaction coordinate (IRC) calculations at the MP2(full)/6‐31G(d) level. The results show that two dyotropic reactions could occur when (CH₃)₂SiHCH₂OH or CH₂?CHSiH₂CH₂OH is heated. One is Brook rearrangement reaction (reaction A), and the dimethylsilyl or vinylsilyl groups migrates from carbon atom to oxygen atom coupled with a simultaneous migration of a hydrogen atom from oxygen atom to carbon atom passing through a double three‐membered ring transition state, forming dimethylmethoxylsilane (CH₃)₂SiHOCH₃ or methoxylvinylsilane CH₂?CHSiH₂OCH₃; the other is a hydroxyl group migration (reaction B) from carbon atom to silicon atom, coupled with a simultaneous migration of a hydrogen atom from silicon atom to carbon atom, via a double three‐membered ring transition state, forming trimethylsilanol (CH₃)₃SiOH or methylvinylsilanol CH₃SiH(OH)CH?CH₂. The G3 barriers of the reactions A and B were computed to be 312.8 and 241.4 kJ/mol for (CH₃)₂SiHCH₂OH, and 317.6 and 233.7 kJ/mol for CH₂?CHSiH₂CH₂OH, respectively. On the basis of the MP2(full)/6‐31G(d) optimized parameters, vibrational frequencies, and G3 energies, the reaction rate constants k(T) and equilibrium constants K(T) were calculated using canonical variational transition state theory (CVT) with centrifugal‐dominant small‐curvature tunneling (SCT) approximation over a temperature range of 400–1800 K. The influences of methyl and vinyl groups attached to the silicon atom on reactions are discussed. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Synthesis,Crystal Structure,and Spectroscopic Characterization of the Borazine Derivatives [B{CH2(SiCl3)}NH]3 and [B{CH2(SiCl2CH3)}NH]3

The borazine derivatives B, B′, B″‐tris[(trichlorosilyl)methyl]borazine [B{CH₂(SiCl₃)}NH]₃ ( 1 ), and B, B′, B″‐tris[{dichloro(methyl)silyl}methyl]borazine [B{CH₂(SiCl₂CH₃)}NH]₃ ( 2 ) were prepared by reacting (Cl₃Si)CH₂(BCl₂) ( 3 ) and [Cl₂(CH₃)Si]CH₂(BCl₂) ( 4 ) with hexamethyldisilazane (hmds), respectively. Both compounds, 1 and 2 crystallize in space group R3c with a = 1712.53(4), c = 1230.33(4) pm, Z = 6, R₁ = 0.030, and a = 1713.8(2), c = 1258.7(2) pm, Z = 6, R₁ = 0.034, respectively. According to the single crystal X‐ray diffraction analyses, the title compounds show a planar B₃N₃ six‐membered ring with B—N distances of 142.3(3) pm (point symmetry C₃) and synfacial oriented substituents. The borazine derivatives have also been characterized by NMR and IR spectroscopy as well as by MS spectrometry.     

Thermochemical properties of free radicals from G3MP2B3 calculations

For a set of 32 selected free radicals, energy minimum structures, harmonic vibrational wave numbers ω_e, principal moments of inertia I_A, I_B, and I_C, heat capacities C°_p(T), entropies S°(T), thermal energy contents H°(T) ? H°(0), and standard enthalpies of formation Δ_fH°(T) were calculated at the G3MP2B3 level of theory in the temperature range 200–3000 K. In this article, thermodynamic functions at T = 298.15 K are presented and compared with recent experimental values. The mean absolute deviation between calculated and experimental Δ_fH°(298.15) values resulted in 3.91 kJ mol^?1, which is close to the average experimental uncertainty of ± 3.55 kJ mol^?1. The influence of hindered rotation on thermodynamic functions is studied for isopropyl and tert‐butyl radicals. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 550–560, 2002     

Electrophilic Alkylations of Vinylsilanes: A Comparison of α‐ and β‐Silyl Effects

Kinetics of the reactions of benzhydrylium ions (Aryl₂CH⁺) with the vinylsilanes H₂C?C(CH₃)(SiR₃), H₂C?C(Ph)(SiR₃), and (E)‐PhCH?CHSiMe₃ have been measured photometrically in dichloromethane solution at 20 °C. All reactions follow second‐order kinetics, and the second‐order rate constants correlate linearly with the electrophilicity parameters E of the benzhydrylium ions, thus allowing us to include vinylsilanes in the benzhydrylium‐based nucleophilicity scale. The vinylsilane H₂C?C(CH₃)(SiMe₃), which is attacked by electrophiles at the CH₂ group, reacts one order of magnitude faster than propene, indicating that α‐silyl‐stabilization of the intermediate carbenium ion is significantly weaker than α‐methyl stabilization because H₂C?C(CH₃)₂ is 10³ times more reactive than propene. trans‐β‐(Trimethylsilyl)styrene, which is attacked by electrophiles at the silylated position, is even somewhat less reactive than styrene, showing that the hyperconjugative stabilization of the developing carbocation by the β‐silyl effect is not yet effective in the transition state. As a result, replacement of vinylic hydrogen atoms by SiMe₃ groups affect the nucleophilic reactivities of the corresponding C?C bonds only slightly, and vinylsilanes are significantly less nucleophilic than structurally related allylsilanes.     

Construction of tetranuclear macrocycles through C-H activation and structural transformation induced by [2+2] photocycloaddition reaction

A series of binuclear complexes [{Cp*Ir(OOCCH₂COO)}₂(pyrazine)] ( 1 b ), [{Cp*Ir(OOCCH₂COO)}₂(bpy)] ( 2 b ; bpy=4,4′‐bipyridine), [{Cp*Ir(OOCCH₂COO)}₂(bpe)] ( 3 b ; bpe=trans‐1,2‐bis(4‐pyridyl)ethylene) and tetranuclear metallamacrocycles [{(Cp*Ir)₂(OOC‐C?C‐COO)(pyrazine)}₂] ( 1 c ), [{(Cp*Ir)₂(OOC‐C?C‐COO)(bpy)}₂] ( 2 c ), [{(Cp*Ir)₂(OOC‐C?C‐COO)(bpe)}₂] ( 3 c ), and [{(Cp*Ir)₂[OOC(H₃C₆)‐N?N‐(C₆H₃)COO](pyrazine)}₂] ( 1 d ), [{(Cp*Ir)₂[OOC(H₃C₆)‐N?N‐(C₆H₃)COO](bpy)}₂] ( 2 d ), [{(Cp*Ir)₂[OOC(H₃C₆)‐N?N‐(C₆H₃)COO](bpe)}₂] ( 3 d ) were formed by reactions of 1 a – 3 a {[(Cp*Ir)₂(pyrazine)Cl₂] ( 1 a ), [(Cp*Ir)₂(bpy)Cl₂] ( 2 a ), and [(Cp*Ir)₂(bpe)Cl₂] ( 3 a )} with malonic acid, fumaric acid, or H₂ADB (azobenzene‐4,4′‐chcarboxylic acid), respectively, under mild conditions. The metallamacrocycles were directly self‐assembled by activation of C? H bonds from dicarboxylic acids. Interestingly, after exposure to UV/Vis light, 3 c was converted to [2+2] cycloaddition complex 4 . The molecular structures of 2 b , 1 c , 1 d , and 4 were characterized by single‐crystal x‐ray crystallography. Nanosized tubular channels, which may play important roles for their stability, were also observed in 1 c , 1 d , and 4 . All complexes were well characterized by ¹H NMR and IR spectroscopy, as well as elemental analysis.     

Theoretical studies of cyclopropylsilylenes: The structures and stability of cyclopropylsilylene C3H5SiH

Ab initio molecular orbital calculations at the G2(MP2) level have been carried out on cyclopropylsilylene C₃H₅SiH. Four equilibrium structures were located. Like H₂Si, the ground state of C₃H₅SiH is singlet and the triplet is the low‐lying excited state. The singlet–triplet separation energy is 127.9 kJ/mol. The cis‐trans isomerization path of singlet cyclopropylsilylene was investigated by intrinsic reaction coordinate (IRC) calculations. The calculations show that no gauche conformers exist along the potential energy curve of the cis‐trans isomerization and the isomerization happens with a barrier of 30.1 kJ/mol. Changes (ΔH and ΔG) in thermodynamic functions, equilibrium constant K(T), and A factor and reaction rate constant k(T) in Eyring transition state theory of the cis‐trans isomerization were also calculated. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Theoretical study of reactions between MH (M=B,Al) and the H2S molecule

Reaction mechanisms between MH (M=B, Al) and the H₂S molecule have been theoretically studied. The G3 ab initio and DFT calculations demonstrate that only one stable addition complex (HM:SH₂, M=B, Al) can be formed, and that, starting from the addition complex (HM:SH₂) two parallel reaction channels have been found: one is an addition reaction to give H₂MSH via the three‐membered ring transition state (TS), and the other is a dehydrogenation reaction to give MSH+H₂ via the four‐membered ring TS. Thermodynamics and Eyring transition state theory (TST) with the Wigner correction are also used to compute the thermodynamic functions, the equilibrium constants, A factors, and the rate constants of these reaction channels at 300–1500 K. The calculated results predict that the product H₂BSH in the system of BH+H₂S and the product AlSH+H₂ in the system of AlH+H₂S will be mainly observed. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Reaktionen eines Dibismutans und von Cyclobismutanen mit Metallcarbonylen ‐ Synthesen von Komplexen mit R2Bi‐, RBi‐, Bi2‐ und Bin‐Liganden (R = Me3CCH2, Me3SiCH2)

Reactions of a Dibismuthane and of Cyclobismuthanes with Metal Carbonyls ‐ Syntheses of Complexes with R₂Bi‐, RBi‐, Bi₂‐ and Bi_n‐ligands (R = Me₃CCH₂, Me₃SiCH₂) Reactions of [Fe₂(CO)₉] with [(Me₃CCH₂)₄Bi]₂ or cyclo‐(Me₃SiCH₂Bi)_n (n = 3 ‐ 5) lead to the complexes [(R₂Bi)₂Fe(CO)₄], [RBiFe(CO)₄]₂[R = Me₃CCH₂, Me₃SiCH₂] and [Bi₂Fe₃(CO)₉]. [Bi₂{Mn(CO)₂C₅H₄CH₃}₃] forms in a photochemical reaction of [Mn(CO)₃C₅H₄CH₃] with cyclo‐(Me₃SiCH₂Bi)_n.     

[2+4] and [2+2] Cycloaddition Reactions of N‐Sulfinyl Carboxylic Acid Amides with (CF3)2BNMe2. Crystal Structure of cyclo‐(CF3)2B‐NMe2‐S(=O)‐N=C(p‐CH3C6H4)‐O

N‐sulfinylacylamides R‐C(=O)‐N=S=O react with (CF₃)₂BNMe₂ ( 1 ) to form, by [2+4] cycloaddition, six‐membered rings cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(R)‐O for R = Me ( 2 ), t‐Bu ( 3 ), C₆H₅ ( 4 ), and p‐CH₃C₆H₄ ( 5 ) while N‐sulfinylcarbamic acid esters R‐O‐C(=O)‐N=S=O react with 1 to yield mixtures of six‐membered (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(OR)‐O) and four‐membered rings (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N(C=O)OR) for R = Me ( 6 and 9 ), Et ( 7 and 10 ), and C₆H₅ ( 8 and 11 ). The structure of 5 has been determined by X‐ray diffraction.     

Synthese und Struktur hochfunktionalisierter 2, 3‐Dihydro‐1H‐1, 3, 2‐diazaborole

Synthesis and Structure of Highly Functionalized 2, 3‐Dihydro‐1H‐1, 3, 2‐diazaboroles A series of differently substituted 2, 3‐dihydro‐1H‐1, 3, 2‐diazaboroles has been prepared by various methods. 1, 3‐Di‐tert‐butyl‐2‐trimethylsilylmethyl‐1H‐1, 3, 2‐diazaborole ( 7 ), 2‐isobutyl‐1, 3‐bis(1‐cyclohexylethyl)‐1H‐1, 3, 2‐diazaborole ( 8 ), 1, 3‐bis‐(1‐cyclohexylethyl)‐2‐trimethylsilylmethyl‐1H‐1, 3, 2‐diazaborole ( 9 ) 1, 3‐bis(1‐methyl‐1‐phenyl‐propyl)‐2‐trimethylsilylmethyl‐1H‐1, 3, 2diazaborole ( 10 ) and 2‐bromo‐1, 3‐bis(1‐methyl‐1‐phenyl‐propyl)‐1H‐1, 3, 2‐diazaborole ( 11 ) were formed by reaction of the corresponding 1, 4‐diazabutadienes with the boranes Me₃SiCH₂BBr₂, iBuBBr₂ and BBr₃ followed by reduction of the resulting borolium salts [R¹ = tBu, Me(cHex)CH, [Me(Et)Ph]C; R² = Me₃SiCH₂, iBu, Br] with sodium amalgam. Treatment of 11 and 12 with silver cyanide afforded the 2‐cyano‐1, 3, 2‐diazaboroles 13 and 14 . An alternative route to compound 8 is based on the alkylation of 2‐bromo‐1, 3, 2‐diazaborole 12 with isobutyllithium. Equimolar amounts of 13 and isobutyllithium give rise to the formation of 15 . The new compounds were characterized by ¹H‐, ¹³C‐, ¹¹B‐NMR, IR and mass spectra. The molecular structures of 7 and meso ‐10 were confirmed by x‐ray structural analysis.     

Theoretical study and rate constants calculation for the reactions X + CF3CH2OCF3 (X = F,Cl, Br)

The multiple‐channel reactions X + CF₃CH₂OCF₃ (X = F, Cl, Br) are theoretically investigated. The minimum energy paths (MEP) are calculated at the MP2/6‐31+G(d,p) level, and energetic information is further refined by the MC‐QCISD (single‐point) method. The rate constants for major reaction channels are calculated by canonical variational transition state theory (CVT) with small‐curvature tunneling (SCT) correction over the temperature range 200–2000 K. The theoretical three‐parameter expressions for the three channels k_1a(T) = 1.24 × 10^?15T^1.24exp(?304.81/T), k_2a(T) = 7.27 × 10^?15T^0.37exp(?630.69/T), and k_3a(T) = 2.84 × 10^?19T^2.51 exp(?2725.17/T) cm³ molecule^?1 s^?1 are given. Our calculations indicate that hydrogen abstraction channel is only feasible channel due to the smaller barrier height among five channels considered. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2012     

Untersuchung der Cokristallisation in den Systemen. Mn(OOCCH3)2-Co(OOCCH3)2-H2O,Mn(OOCCH3)2-Ni(OOCCH3)2-H2O,Mn(OOCCH3)2-Zn(OOCCH3)2-H2O bei 60°C

Investigation of Cocrystallization in the Systems Mn(OOCCH₃)₂-Co(OOCCH₃)₂-H₂O, Mn(OOCCH₃)₂-Ni(OOCCH₃)₂-H₂O, Mn(OOCCH₃)₂-Zn(OOCCH₃)₂-H₂O at 60°C The three-component systems Mn(OOCCH₃)₂-Co(OOCCH₃)₂-H₂O, Mn(OOCCH₃)₂-Ni(OOCCH₃)₂-H₂O and Mn(OOCCH₃)₂-Zn(OOCCH₃)₂-H₂O at 60°C were investigated by physio-chemical analysis. There is an interruption in the series of mixed crystals formed in the three-component systems. The inclusion of Co²⁺- and Ni²⁺ in Mn(OOCCH₃)₂ · 2 H₂O of Mn²⁺ in Co(OOCCH₃)₂ · 2 H₂O, Zn(OOCCH₃)₂ · 2 H₂O and Ni(OOCCH₃)₂ · 4 H₂O is based on isodimorphic substitution. It was found that in the system Mn(OOCCH₃)₂-Zn(OOCCH₃)₂-H₂O crystallizes Zn(OOCCH₃)₂ · Mn(OOCCH₃)₂ · 2 H₂O. It was identified by the X-ray and differential thermal analysis.     

Aluminiumhydrazide. Bildung eines dimeren Di(tert‐butyl)aluminiumhydrazids mit viergliedrigem Al2N2‐Heterozyklus und Umsetzung eines Dialkylaluminiumchlorids mit Dilithium‐bis(trimethylsilyl)hydrazid

Aluminium Hydrazides – Formation of a Dimeric Di( tert ‐butyl)aluminium Hydrazide Containing a Four‐Membered Al₂N₂ Heterocycle and Reaction of Dialkylaluminium Chloride with Dilithium Bis(trimethylsilyl)hydrazide The reaction of di(tert‐butyl)aluminium chloride with tert‐butylhydrazine yielded an adduct ( 1 ) which was isolated in a pure form and characterized by crystal structure determination. 1 reacted with n‐butyllithium by deprotonation and salt elimination to give the corresponding di(tert‐butyl)aluminium hydrazide ( 2 ), which is a dimer in solution and in the solid state and possesses a four‐membered Al₂N₂ heterocycle with two exocyclic N–N bonds. The structure of 2 differs from that of other di(tert‐butyl)aluminium hydrazides which have four‐ or five‐membered heterocycles. Treatment of impure samples of 1 with n‐butyllithium yielded by the cleavage of the N–N bonds a mixture of several unknown products, from which the dimeric, centrosymmetric aluminium amide [(Me₃C)₂AlN(H)CMe₃]₂ ( 3 ) was isolated. A similar product ( 4 ) was obtained in a low yield by the reaction of (Me₃SiCH₂)₂AlCl with the dilithium hydrazide Li₂N₂(SiMe₃)₂. An intact N–N bond was neither found in the second product isolated from this reaction. Instead a tricyclic compound was formed by C–H activation which has two five‐membered AlNSiC₂ heterocycles bridged by Al–N bonds.     

Stereoselective Construction of 1,3‐Disilylcyclopentane Derivatives by Scandium‐Catalyzed [3+2] Cycloaddition of Allylsilanes to β‐Silylenones

The Sc(OTf)₃‐catalyzed [3+2] cycloaddition of allylsilanes to β‐silyl‐α,β‐unsaturated ketones (β‐silylenones) has been developed to form five‐membered syn‐1,3‐disilylketones diastereoselectively through the rearrangement of the silicon substituents on the allylsilane. Stabilization of the carbocation intermediates by a double silicon effect plays a key role in directing the course of the reaction to favor the [3+2] cycloaddition pathway over simple allylation.     

A rhodium(III) complex of the linear diborazine H3B·NMe2BH2·NMe2H: an intermediate in the dehydrocoupling of H3B·NMe2H

The solid‐state structure of the rhodium complex (dimethylamine–dimethylaminoborane–borane‐κ²H,H′)dihydridobis(triisopropylphosphane‐κP)rhodium(III) tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate, [RhH₂(C₄H₁₈B₂N₂)(C₉H₂₁P)₂](C₃₂H₁₂BF₂₄), is reported. The complex contains the linear diborazine H₃B·NMe₂BH₂·NMe₂H, a kinetically important intermediate in the transition‐metal‐mediated dehydrocoupling of H₃B·NMe₂H, ultimately affording the dimeric amino‐borane [H₂BNMe₂]₂. The structure of the title complex contains a distorted octahedral Rh^III centre, with mutually trans phosphane ligands and cis hydride ligands. The diborazine is bound through two Rh—H—B σ‐bonds and exhibits a gauche conformation with respect to the B—N—B—N backbone.     

μ3‐η2:η2:η2‐Coordination of Primary Silane on a Triruthenium Plane

A μ₃‐η²:η²:η²‐silane complex, [(Cp*Ru)₃(μ₃‐η²:η²:η²‐H₃SitBu)(μ‐H)₃] ( 2 a ; Cp*=η⁵‐C₅Me₅), was synthesized from the reaction of [{Cp*Ru(μ‐H)}₃(μ₃‐H)₂] ( 1 ) with tBuSiH₃. Complex 2 a is the first example of a silane ligand adopting a μ₃‐η²:η²:η² coordination mode. This unprecedented coordination mode was established by NMR and IR spectroscopy as well as X‐ray diffraction analysis and supported by a density functional study. Variable‐temperature NMR analysis implied that 2 a equilibrates with a tautomeric μ₃‐silyl complex ( 3 a ). Although 3 a was not isolated, the corresponding μ₃‐silyl complex, [(Cp*Ru)₃(μ₃‐η²:η²‐H₂SiPh)(H)(μ‐H)₃] ( 3 b ), was obtained from the reaction of 1 with PhSiH₃. Treatment of 2 a with PhSiH₃ resulted in a silane exchange reaction, leading to the formation of 3 b accompanied by the elimination of tBuSiH₃. This result indicates that the μ₃‐silane complex can be regarded as an “arrested” intermediate for the oxidative addition/reductive elimination of a primary silane to a trinuclear site.     

Organometallic Polyelectrolytes: Synthesis,Characterization and Layer‐By‐Layer Deposition of Cationic Poly(ferrocenyl(3‐ammoniumpropyl)‐methylsilane)

The water soluble poly(ferrocenylsilane) polycation, poly(ferrocenyl(3‐ammoniumpropyl)methylsilane), was synthesized by transition metal‐catalyzed ring‐opening polymerization of the novel [1]ferrocenophane Fe(η‐C₅H₄)₂SiCH₃(CH₂)₃Cl and by subsequent side group modification. Amination of the chloropropyl moieties using potassium 1,1,3,3‐tetramethyldisilazide followed by acidic hydrolysis produced the polycation. The polycation was employed together with poly(sodium vinylsulfonate) in the electrostatic layer‐by‐layer self‐assembly process to form organometallic multilayers on quartz. The multilayer fabrication process was monitored using UV/Vis absorption spectroscopy and XPS.     

Photocurrent Enhancement in Diketopyrrolopyrrole Solar Cells by Manipulating Dipolar Anchoring Terminals on Alkyl‐Chain Spacers

We chose DPP‐BDT‐DPP {DPP=diketopyrrolopyrrole, BDT=4,8‐di‐[2‐(2‐ethylhexyl)‐thienyl]benzo[1,2‐b:4,5‐b′]dithiophene} as a model backbone and varied the anchoring groups [? C₅H₁₁, ? COOCH₃, and ? SiCH₃(OSiCH₃)₂] terminated on the N‐substituted alkyl‐chain spacer of the DPP units to study the effect of anchoring terminals on the morphology of blend film and on the device performances of bulk heterojunction solar cells. By replacing the nonpolar ? C₅H₁₁ anchoring terminal with the polar ? COOCH₃ anchoring terminal leads to an enhancement in the short‐circuit current density (J_sc) (4.62 vs. 9.32 mA cm^?2), whereas the value of J_sc sharply decreases to 0.45 mA cm^?2 if the ? C₅H₁₁ anchoring terminal is replaced by a ? SiCH₃(OSiCH₃)₂ group. The changes in J_sc are associated with changes in the π–π stacking distance (3.39→3.34 Å vs. 3.39→3.45 Å) and the phase size (50→20 nm vs. 50→>250 nm) through alteration of the anchoring group from ? C₅H₁₁ to ? COOCH₃ versus from ? C₅H₁₁ to ? SiCH₃(OSiCH₃)₂. Interestingly, the anchoring terminals bring about drastic changes in molecular orientations, which result in different out‐of‐plane hole transport. This is the first time this effect has been systemically demonstrated to improve photocurrent generation by manipulating the dipolar anchoring groups terminated on the alkyl‐chain spacer.     

Structure,Stereochemistry and Dynamics of Tetranuclear Polyhydride Clusters Containing Chiral Heterobidentate Phosphanes

A novel chiral phosphane (S)‐2‐(4‐isopropyl‐2‐oxazoline‐2‐yl)phenyl‐di‐N‐pyrrolylphosphane (S‐PyrPOx) based on asymmetric oxazoline ring has been prepared and characterised. Reaction of this ligand and its phenyl‐substituted analogue (S‐PhPOx) with H₄Ru₄(CO)₁₂ and H₃RhOs₃(CO)₁₂ gave substituted derivatives H₄Ru₄(CO)₁₀(1,1‐PhPOx) ( 2 ), H₄Ru₄(CO)₁₀(1,1‐PyrPOx) ( 3 ), and H₃RhOs₃(CO)₁₀(1,1‐PyrPOx) ( 4 ), which were structurally characterised by X‐ray crystallography in solid state and by a variety of multinuclear NMR spectroscopic measurements in solution. In all studied clusters the coordinated ligands form five‐membered chelate rings through phosphorus and nitrogen atoms of oxazoline moiety to afford a novel chiral center associated with the substituted metal atom. The substitution reactions demonstrate extremely high stereoselectivity, which results in formation of only one diastereomer in all three cases to give S,S isomer in 2 and S,R isomer in 3 and 4 .