Das iso-Tetraphosphan P[P(SiMe3)Me]2[P(SiMe3)2]

H ? C Bond Cleavage in Ferrocene by Organylruthenium Complexes Cp*(Me₃P)₂RuCH₂CMe₃ ( 1 ) reacts at 85°C with ferrocene ( 2 ) by cleavage of one H? C bond in 2 to give CpFe[η⁵-C₅H₄Ru(PMe₃)₂Cp*] ( 3 ) (Cp = η⁵-C₅H₅; Cp* = η⁵-C₅Me₅) and neopentane. The ruthenium atom in 3 has a distorted tetrahedral geometry, the planar Cp ligands in the ferrocenyl fragment are eclipsed. Solutions of 3 in [D₆]benzene or [D₈]THF exhibit H? D exchange of the ferrocenyl protons. In the [D₈]THF molecule only the α-deuterium atoms are exchanged. Reaction pathways for this exchange are discussed.     

Bildung und Struktur des iso-Tetraphosphans P(PtBu2)3: ein Molekül mit einem planaren,dreibindigen P-Atom

Formation and Structure of the iso -Tetraphosphane P(P^tBu₂)₃: a Molecule with a Planar Three-coordinated P Atom The iso-tetraphosphane P(P^tBu₂)₃ ( 1 ) was obtained by irradiating ^tBu₂P–P=P(Me)^tBu₂ ( 3 ). 1 forms hexagonal crystals (space group P6₃/m) with a = 1005,63(8), c = 1621,4(2) pm, Z = 2. The P(P^tBu₂)₃ molecules are arranged in a hexagonally close packed lattice. The four P atoms in each molecule are coplanar with P–P bond distances 219.08(4) pm and P–P–P angles 120°. The observed planar geometry is in accordance with ab initio calculations.     

Bildung und struktur der Cyclophosphane P4(CMe3)2[P(CMe3)2]2 und P4(SiMe3)2[P(CMe3)2]2

Formation and Structure of the Cyclophosphanes P₄(CMe₃)₂[P(CMe₃)₂]₂ and P₄(SiMe₃)₂[P(CMe₃)₂]₂ n-Triphosphanes showing a SiMe₃ and a Cl substituent at the atoms P¹ and P², like (Me₃C)₂P? P(SiMe₃)? P(CMe₃)Cl 3 or (Me₃C)₂P? P(Cl)? P(SiMe₃)₂ 4 are stable only at temperatures below ?30°C. Above this temperature these compounds lose Me₃SiCl, thus forming cyclotetraphosphanes, P₄(CMe₃)₂[P(CMe₃)₂]₂ 1 out of 3 , P₄(SiMe₃)₂[P(SiMe₃)₂]₂ 2a (cis) and 2b (trans) out of 4 . The formation of 1 proceeds via (Me₃C)₂P? P?PCMe₃ 5 as intermediate compound, which after addition to cyclopentadiene to give the Diels-Alder-adduct 6 (exo and endo isomers) was isolated. 6 generates 5 , which then forms the dimer compound 1 . Likewise (Me₃C)₂P? P?P-SiMe₃ 8 (as proven by the adduct 7 ) is formed out of 4 , leading to 2a (cis) and 2b (trans). Compound 1 is also formed out of the iso-tetraphosphane P[P(CMe₃)₂]₂[P(CMe₃)Cl] 9 , which loses P(CMe₃)₂Cl when warmed to a temperature of 20°C. 1 crystallizes monoclinically in the space group P2₁/a (no. 14); a = 1762.0(15) pm; b = 1687.2(18) pm; c = 1170.5(9) pm; β = 109.18(5)° and Z = 4 formula units in the elementary cell. The molecule possesses E conformation. The central four-membered ring is puckered (approx. symmetry 4 2m; dihedral angle 47.4°), thus bringing the substituents into a quasi equatorial position and the nonbonding electron pairs into a quasi axial position. The bond lengths in the four-membered ring of 1 (d (P? P) = 222.9 pm) are only slightly longer than the exocyclic bonds (221.8 pm). The endocyclic bond angles \documentclass{article}\pagestyle{empty}\begin{document}$ \bar \beta $\end{document}(P/P/P) are 85.0°, the torsion angles are ±33° and d (P? C) = 189.7 pm.     

Komplexchemie at P-reicher Phosphane und Silylphosphane. VI. Bildung und Struktur der Chromcarbonylkomplexe des Tris(trimethylsilyl) heptaphosphanortricyclans (Me3Si)3P7

Formation and Structures of Chromium Carbonyl Complexes of Tris(trimethylsily)heptanortricyclane (Me₃Si)₃P₇ (Me₃Si)₃P₇ 1 reacts with one equivalent of Cr(Co)₅THF 2 to give the yellow (Me₃Si)₃P₇[Cr(Co)₅] 4. The Cr(Co)₅group is attached to a P^e atom. Yellow (Me₃Si)₃P₇[Cr(CO)₅]₂ 5 is obtained either from reacting 1 with two equivalents of 2 , or from 4 with one equivalent of 2. One Cr(CO)₅ groups in 5 is coordinated to a P^e atom, the other one to a P,^b atom. Similarly, Yellow (Me₃Si)₃P₇[Cr(CO)₅]₃ 6 results from reacting 5 with one equivalent of 2 . Two Cr(CO)₅ groups in 6 are linked to P^b atoms, and the third one either to a P^e or the P^a atom (assignment not completely clear). Derivatives containing a P^e bridge appear in reactions of 1 with higher amounts of 2 . Such, 5 forms mixtures of the red compounds (Me₃Si)₃P₇ × [Cr(CO)₅]₂[Cr(CO)₄] 8 and (Me₃Si)₃P₇[Cr(CO)₅] × [Cr(CO)₄] 9 , and even preferably 9 with four equivalents of 2 . In 8 , one Cr(CO)₅ group is attached to that p^e atom which is not engaged in the Cr(CO)₄ bridge, and the second to one of the P^b atoms directly adjacent to the bridge. The additional Cr(CO)₅ group in 9 is coordinated to the remaining P^b atom directly adjacent to the bridge. In reactions of 5 with even higher amounts of 2 , four Cr(CO)₅ groups and one Cr(CO)₄ bridge attach to the basic P₇ skeleton to from the less stable Me₃P₇[Cr(CO)₅]₄[Cr(CO)₄]. (Me₃Si)₃P₇ 1 reacts considerably slower with Cr(CO)₅THF 2 than R₃P₇ (R = Et, iPr). Cr(CO)₄NBD 3 reacts with 1 , but it was not possible to isolate (Me₃Si)₃P₇[Cr(CO)₄]. However, 4 with 3 forms (Me₃Si)₃P₇[Cr(CO)₅][Cr(CO)₄] 7 , and 5 with 3 yields (Me₃Si)₃P₇[Cr(CO)₅]₂[Cr(CO)₄] 8 . The structures of 4 , 5 , 7 , 8 or 9 are quite analogous to those of the derivatives of Et₃P₇ but there exist significant differences in stability and reactivity. While Et₃P₇[Cr(CO)₅]₂ in solution rearranges to give the stable Et₃P₇[Cr(CO)₅][Cr(CO)₄], the analogous (Me₃Si)₃P₇[Cr(CO)₅][Cr(CO)₄] 7 is not stable and is not obtained from (Me₃Si)₃P₇[Cr(CO)₅]₂ 5 . Et₃P₇[Cr(CO)5]₃ can just be detected spectroscopically and rearranges easily to give Et₃P₇[Cr(CO)₅]₂ [Cr(CO)₄] whereas (Me₃Si)₃P₇[Cr(CO)₅]₃ 6 can be isolated. These differences are caused by the greater steric requirements of Me₃Si groups. The formation of a P^e–Cr(CO)₄–P^e bridge, e.g., requires a Me₃Si group in 1 to switch from the s to the as position. Whereas many of the complex compounds of R₃P₇ (R = Et, iPr) crystallize easily, the analogous derivatives of (Me₃Si)₃P₇ did not yield crystals. The structures of the products were assigned by evaluating the coordination shift in their ₃₁P NMR spectra and by comparision of these spectra with those of such derivatives of Et₃P₇ which previously had been investigated by single crystal structure determinations.     

Einfluß der Ringatome auf die Struktur von Triel‐Pentel‐Heterozyklen – Synthese und Molekülstrukturen von [Me2InAs(SiMe3)2]2 und [Me2InSb(SiMe3)2]3

Influence of the Ring Atoms on the Structure of Triel‐Pentel Heterocycles – Synthesis and X‐Ray Crystal Structures of [Me₂InAs(SiMe₃)₂]₂ and [Me₂InSb(SiMe₃)₂]₃ Triel‐pentel heterocycles [Me₂InE(SiMe₃)₂]_x have been prepared by dehalosilylation reactions from Me₂InCl and E(SiMe₃)₃ (E = As, x = 2; E = Sb, x = 3) and characterised by NMR spectroscopy and by X‐ray crystal structure analyses. In addition the X‐ray crystal structures of [Me₂GaAs(SiMe₃)₂]₂ and [Me₂InP(SiMe₃)₂]₂ are reported. The compounds complete a family of 13 identically substituted heterocycles [Me₂ME(SiMe₃)₂]_x (M = Al, Ga, In; E = N, P, As, Sb, Bi; x = 2, 3), whose structures were investigated depending on the ring atoms M and E. The tendencies that have been observed concerning the ring sizes can be explained by the interplay of the atomic radii of the central atoms and the sterical demand of the ligands. After a formal separation of the M–E bonds in σ bonds and dative bonds the characteristic differences and trends in the endocyclic and exocyclic bond angles of both centres M and E can be interpreted on the basis of a simple Lewis acid/base adduct model.     

Bildung siliciumorganischer Verbindungen. 92 [1]. Bildung und Struktur des Oktamethyl-hexasila-hexascaphans

Formation of Organosilicon Compounds. 92. Formation and Structure of Octamethylhexasila-hexascaphane By rearrangement and abstraction of CH₄ at the presence of AlBr₃ 2 forms 3 , and 6 forms 7 , which is also obtained reacting 8 and 9 under the same condition. Lithination of 1, 1, 3, 5, 5, 7, 7, 9, 9-Nonamethyl-1, 3, 5, 7, 9-pentasiladecaline yields 12 , which is trapped with me₃SiCl to form 6 . Convertation of 13 to 14 leads to 8 by reaction with ClSi(CH₂—Sime₃)₃. Compound 7 is characterized by NMR and mass spectroscopy as well as X-ray structural analysis. 1, 3, 5, 7, 9, 9, 11, 11-Octamethyl-1, 3, 5, 7, 9, 11-hexasila-hexascaphane 7 crystallizes in the monoclinic space group P2₁/n (No. 14) with a = 3296.7 pm, b = 1536.2 pm, c = 891.9 pm, β 91.71° and Z = 8 formular units. Both crystallographic independent molecules have approximately the symmetry C₂. The differences of corresponding bond lengths, bond angles and torsion angles are unimportant. But there is a distinct dependence of the Si? C bond length relative to the function of the bond in the molecule (Averages: Si? C) (endo) = 188.4 pm, Si? C (exo) = 187.6 (pm).     

Komplexchemie P-reicher Phosphane und Silylphosphane. VII [1]. Bildung und Struktur von [Li(DME)3]2{(SiMe3)[Cr(CO)5]2 P?PP?P[Cr(CO)5]2(SiMe3)}

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. VII. Formation and Structure of [Li(DME)₃]₂{(SiMe₃)[Cr(CO)₅]₂ P-P ? P-P[Cr(CO)₅]₂(SiMe₃)} Deep red crystals of the title compound 1 are produced in the reaction of LiP(Me₃Si)₂[Cr(CO)₅] with 1, 2-dibromoethane in DME. The structure of 1 was derived from the investigation of the ³¹P-NMR spectra and confirmed by a single crystal structure determination. 1 crystallizes in the space group P1 (no. 2); a = 1307.8(5)pm, b = 1373.1(5)pm, c = 1236.1(4)pm, α = 106.22(4)°, β = 88.00(3)°, γ = 115.52(4)° and Z = 1. 1 forms a salt composed of a dianion R₂R₄′P₄^2? (R ? SiMe₃, R′ ? Cr(CO)₅) and solvated Li⁺ cations. The zigzag shaped dianion possesses the symmetry 1 -C_i. The distances d(P? P) = 202.5(1)pm and d(P? P) = 221.9(1)pm correspond to a double bond and single bonds, respectively. The distances d(Cr? P) = 251.1(1) pm and 255.3(1) pm are larger than those observed so far which might be caused by the charge distribution in the dianion.     

[iPr2P]2P?SiMe3 und [iPr2P]2PLi – Synthese und Reaktionen Struktur des [iPr2P]2P?P[PiPr2]2

[iPr₂P]₂P? SiMe₃ and [iPr₂P]₂PLi – Synthesis and Reactions Structure of [iPr₂P]₂P? P[PiPr₂]₂ [iPr₂P]₂P? SiMe₃ 1 and [iPr₂P]₂PLi 2 were prepared to investigate the influence of the bulky alkyl groups on formation and properties of the ylides R₂P? P?P(X)R₂ (R = iPr, tBu; X = Br, Me) in reactions of 1 with CBr₄ and of 2 with 1,2-dibromoethane or MeCl, resp. Compared to the iPr groups the tBu groups favour the formation of ylides. With CBr₄ 1 forms iPr₂P? P?P(Br)iPr₂ 5 just as a minor product which decomposes already below ?30°C. With 1,2-dibromoethane 2 yields only traces of 5 but [iPr₂P]P? P[P(iPr)₂]₂ 7 as main product. With MeCl 2 gives iPrP? P?P(Me)iPr₂ 9 and [iPr₂P]₂PMe 10 in a molar ratio of 1:1. 9 is considerably more stable than 5. 7 crystallizes triclinic in the space group P1 (No. 2) with a = 10.813 Å, b = 11.967 Å, c = 15.362 Å, α = 67.90°, β = 71.36°, γ = 64.11° and two formula units in the unit cell.     

Kristallstruktur des Zinkamids Zn[N(SiMe3)2]2

Crystal Structure of the Zinc Amide Zn[N(SiMe₃)₂]₂ X‐ray quality crystals of Zn[N(SiMe₃)₂]₂ (monoclinic, P2₁/c) are obtained by sublimation of the zinc amide Zn[N(SiMe₃)₂]₂ at —30 °C in vacuo (300 torr). According to the result of the X‐ray structural analysis, Zn[N(SiMe₃)₂]₂ contains an almost linear N‐Zn‐N unit with two short N‐Zn bonds.     

Bildung und Struktur des [{cyclo‐P4(PtBu2)4}{Ni(CO)2}2]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXVI. Formation and Structure of [{ cyclo ‐P₄(P^tBu₂)₄}{Ni(CO)₂}₂] [{cyclo‐P₄(P^tBu₂)₄}{Ni(CO)₂}₂] is formed by reaction of the cyclotetraphosphane P₄(P^tBu₂)₄ with [Ni(CO)₄]. Each Ni(CO)₂ unit is coordinated by two adjacent ^tBu₂P groups forming two five‐membered P₄Ni rings above and below the planar cyclotetraphosphane ring, respectively. The compound crystallizes in the triclinic space group P 1 (No. 2) with a = 893.29(5), b = 1140.75(7), c = 1235.52(8) pm, α = 109.179(7), β = 100.066(7), γ = 97.595(7)° and Z = 1.     

Komplexchemie P-reicher Phosphane und Silylphosphane. IV. Bildung und Struktur der Chromcarbonylkomplexe des Tris(di-tert-butylphospha)heptaphosphanortricyclans, (t-Bu2P)3P7

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. IV. Formation and Structure of the Chromium Carbonyl Complexes of Tris(di-tert-butylphospha)heptaphosphanortricyclane (t-Bu₂P)₃P₇ The reaction of (t-Bu₂P)₃P₇ 1 with Cr(CO)₅ · THF in a molar ratio of 1:1 yields yellow crystals of (t-Bu₂P)₃P₇[Cr(CO)₅] 2 having the Cr(CO)₅ group coordinated to a P^b atom (basal) of the three membered ring. With a molar ratio of 1:2 compounds 2 , (t-Bu₂P)₃P₇[Cr(CO)₅]₂ 3 , (t-Bu₂P)₃P₇[Cr(CO)₅][Cr(CO)₄] 4 and (t-Bu₂P)₃P₇[Cr(CO)₄]₂ 5 were obtained. In 3 (yellow crystals) one Cr(CO)₅ group is linked to a P^b atom, the other one to an exocyclic P^exo atom. On irradiation 3 loosing one CO group generates 4 (orange red crystals) with an unchanged Cr(CO)₅ group linked to the Pb atom and a five membered chelate-like ring containing an apical Pa atom, two equatorial P^a atoms, one P^exo atom and the Cr atom of the carbonyl group. Compound 5 (orange red crystals) contains two such five membered rings. (t-Bu₂P)₃P₇[Cr(CO)₄]₃ 6 (red needles) is formed with Cr(CO)₅ · THF in a molar ratio of 1 : 1. However, even with higher amounts of Cr(CO)₅ · THF and after extended reaction times, only 6 is formed; no further Cr carbonyl group could be attached to the P skeleton. With Cr(CO)₅ · NBD in a molar ratio of 1 : 1, (t-Bu₂P)₃P₇[Cr(CO)₄] 7 is produced from 1, and 5 with a molar ratio of 2 : 1. As in 4, the Cr(CO)₄ group in 7 (orange crystals) participates in a five membered chelate-like ring. It was not possible to generate 6 from 5 with an excess of Cr(CO)₄ · NBD and with extended reaction times. The molecular structures of the compounds were identified by investigating the ³¹P[¹H] NMR spec-tra and considering especially the coordination shift, and by crystal structure determinations of 2 and 4. Compound 2 crystallizes in the space group PI (no.2) with a = 1566.2(4) pm, b = 2304.1(5) pm, c = 1563.3(4) pm,α = 95.57(3)°, β = 108.79(3)°, γ = 109.82(4)° and Z = 4 formula units in the elementary cell. Compound 4 crystallizes in the space group P 2₁ /n (no. 14) with a = 1416.6(5) pm, b = 2573.6(5) pm, c = 1352.9(4) pm,β = 99.17(5)° and Z = 4 formula units in the elementary cell.     

Synthese und Struktur eines Pentaalkylchlorohexastibans Sb6R5Cl [R = (Me3Si)2CH]

Synthesis and Structure of Pentaalkylchlorohexastibane Sb₆R₅Cl [R = (Me₃Si)₂CH] The reaction of RSbCl₂ [R = (Me₃Si)₂CH] with Na‐K alloy in tetrahydrofuran gives besides the known rings Sb_nR_n (n = 3, 4), (Me₃Si)₂CH₂ and the pentaalkylchlorohexastibane Sb₆R₅Cl ( 1 ). 1 was characterized by spectroscopic methods (MS, ¹H‐, ¹³C‐NMR, X‐ray diffraction). The structure of 1 consists of a folded four membered antimony ring in the all‐trans configuration with three alkyl groups and one Sb(R)—Sb(R)Cl fragment as substituents.     

Neue viergliedrige GaE‐ und InE‐Ringverbindungen: Synthese und Kristallstruktur von [Et2InE(SiMe3)2]2 und [GaCl(PtBu2Me)E(SiMe3)]2 (E = P,As)

New GaE and InE Four Membered Ring Compounds: Syntheses and Crystal Structures of [Et₂InE(SiMe₃)₂]₂ and [GaCl(P t Bu₂Me)E(SiMe₃)]₂ (E = P, As) Et₃In · PR₃ (R = Et, iPr) reacts with H₂ESiMe₃ under liberation of C₂H₆ and EH₃ to form the cyclic compounds [Et₂InE(SiMe₃)₂]₂ ( 1 a : E = P, 1 b : E = As). 1 consists of a planar four membered In₂E₂ ring in which the indium and phosphorus or arsenic atoms are four coordinated. In contrast, the phosphorus/arsenic atoms in [GaCl(PtBu₂Me)E(SiMe₃)]₂ ( 2 a : E = P, 2 b : E = As) only have the coordination number three. 2 results from the reaction of GaCl₃ · PtBu₂Me with As(SiMe₃)₃ or Li₂PSiMe₃ respectively, and displays a folded four membered Ga₂E₂ ring as central structural motif. 1 and 2 have been characterised by single crystal X‐ray diffraction analysis as well as ¹H and ³¹P{¹H} NMR spectroscopy.     

Bildung siliciumorganischer Verbindungen. 85 [1]. Bildung,Reaktionen und Struktur des 1,1,3,3-Tetramethyl-2,4-bis(trimethylsilyl)-1,3-disilabicyclo[1, 1, 0]butans

me₃Si? CCl₂?Sime₂Cl (me ? CH₃) läßt sich mit n-buLi (bu ? C₄H₉) bei–100°C (Lösungsmittel THF/Äther) in me₃Si? CCl(Li)? Sime₂Cl a überführen. das mit meJ me₃Si? CClme? Sime₂Cl bildet. Wird a in Abwesenheit eines Abfangreagenzes langsam erwärmt, so bildet sich unter Abspaltung von LiCl (Cl aus der SiCl-Gruppe) über eine reaktive Zwischenstufe des Bicyclobutans b . Die Struktur von b ist durch NMR-Untersuchung, Röntgenstrukturanalyse und Abbaureaktionen gesichert. Mit HBr bzw. CH₃OH werden die Si? C-Bindungen der Dreiringe in b gespalten, so daß sich me₃Si? CH₂? C(Sime₂X)₂Sime₃ (X ? Br, OCH₃) bildet. Formation of Organosilicon Compounds. 85. Formation, Reactions, and Structure of 1,1,3,3-Tetramethyl-2,4-bis(trimethylsilyl)-1,3-disilabicyclo[1, 1, 0]butane me₃Si? CCl₂? Sime₂Cl (me ? CH₃) with n-buLi (bu ? C₄H₉) at –100°C (solvent: THF/ether) yields me₃Si? CCl(Li)? Sime₂Cl a , which forms me₃Si? CClme? Sime₂Cl with meI. By warming a slowly in absence of any trapping reagent the bicyclobutane b is obtained via a reactive intermediate under elimination of LiCl (Cl from the SiCl group). The structure of b is established by nmr investigations, X-ray structure determination and chemical derivatisation.     

Zur Bildung der Cyclotetraphosphane cis- und trans-P4(SiMe3)2(CMe3)2 bei der Umsetzung von (Me3C)PCl2 mit LiP(SiMe3)2 · 2 THF

Formation of the Cyclotetraphosphanes cis- und trans-P₄(SiMe₃)₂(CMe₃)₂ in the Reaction of (Me₃C)PCl₂ with LiP(SiMe₃)₂ · 2 THF The mechanism of the reaction of (Me₃C)PCl₂ 1 with LiP(SiMe₃)₂ · 2 THF 2 was investigated. With a mole ration of 1:1 at ?60°C quantitatively (Me₃C)(Cl)P? P(SiMe₃)₂ 3 is formed. This compound eliminates Me₃SiCl on warming to 20°C, yielding Me₃Si? P?P? CMe₃ 4 (can be trapped using 2,3-dimethyl-1,3-butadiene in a 4+2 cycloaddition), which dimerizes to produce the cyclotetraphosphanes cis-P₄(SiMe₃)₂(CMe₃)₂ 5 and trans-P₄(SiMe₃)₂(CMe₃)₂ 6 . Also with a mole ratio of 1:2 initially 3 is formed which remarkably slower reacts on to give [(Me₃Si)₂P]P₂P? CMe₃ 8 . Remaining LiP(SiMe₃)₂ cleaves one Si? P bond of 8 producing (Me₃)₂P? P(CMe₃)? P(SiMe₃)₂Li. Via a condensation to the pentaphosphide 10 and an elimination of LiP(SiMe₃)₂ from this intermediate, eventually trans-P₄(SiMe₃)₂(CMe₃)₂ 6 is obtained as the exclusive cyclotetra-phosphane product.     

Studien zur Reaktion von [Me2AlP(SiMe3)2]2 mit basenstabilisierten Organogalliumchloriden und ‐hydriden

Investigations on the Reactivity of [Me₂AlP(SiMe₃)₂]₂ with Base‐stabilized Organogalliumhalides and ‐hydrides [Me₂AlP(SiMe₃)₂]₂ ( 1 ) reacts with dmap?Ga(Cl)Me₂, dmap?Ga(Me)Cl₂, dmap?GaCl₃ and dmap?Ga(H)Me₂ with Al‐P bond cleavage and subsequent formation of heterocyclic [Me₂GaP(SiMe₃)₂]₂ ( 2 ) as well as dmap?AlMe_xCl_3?x (x = 3 8 ; 2 3 ; 1 4 ; 0 5 ). The reaction between equimolar amounts of dmap?Al(Me₂)P(SiMe₃)₂ and dmap?Ga(t‐Bu₂)Cl yield dmap?Ga(t‐Bu₂)P(SiMe₃)₂ ( 6 ) and dmap?AlMe₂Cl ( 3 ). 2 – 8 were characterized by NMR spectroscopy, 2 and 6 also by single crystal X‐ray diffraction.