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The reactions of [N3P3Cl6] with one, two, or three equivalents of the difunctional 1,2-closo-carborane C2B10H10{CH2OH}2 and K2CO3 in acetone have been investigated. These reactions led to the new spiro-closo-carboranylphosphazenes gem-[N3P3Cl6−2n{(OCH2)2C2B10H10}n] (n=1 (1), 2 (2)) and the first fully carborane-substituted phosphazene gem-[N3P3{(OCH2)2C2B10H10}3] (3). A bridged product, non-gem-[N3P3Cl4{(OCH2)2C2B10H10}] (4), was also detected. The reaction of the well- known spiro derivatives [N3P3Cl2(O2C12H8)2] and [N3P3Cl4(O2C12H8)] with the same carborane-diol and K2CO3 in acetone gave the new compounds gem-[N3P3(O2C12H8)3−n{(OCH2)2C2B10H10}n] (n=1 (5) or 2 (6), respectively), without signs of intra- or intermolecularly bridged species. Upon treatment with NEt3 in acetone, compound 5 was converted into the corresponding nido-carboranylphosphazene. However, the reaction of gem-[N3P3(O2C12H8)2{(OCH2)2C2B10H10}] (5) with NEt3 in ethanol instead of acetone proceeded in a different manner to give the new compound (NHEt3)2[N3P3(O2C12H8)2(O){OCH2C2B9H10CH2OCH2CH3}] (7). For compounds with two 2,2'-dioxybiphenyl units, gem-[N3P3(O2C12H8)2{(OCH2)2C2B10H10}] (5), (NHEt3)[N3P3(O2C12H8)2{(OCH2)2C2B9H10}] (8), and (NHEt3)2[N3P3(O2C12H8)2(O){OCH2C2B9H10CH2OCH2CH3}] (7), a mixture of different stereoisomers may be expected. However, for 5 and 7 only the meso compounds seem to be formed, with the same (R,S)-configuration as in the precursor [N3P3Cl2(O2C12H8)2]. The reaction of 5 to give 8 seems to proceed with a change of configuration at one phosphorus center, giving a racemic mixture. The crystal structures of the nido-carboranylphosphazenes 7 and 8 have been confirmed by X-ray diffraction methods.

The reactions of [N3P3Cl6] with one, two, or three equivalents of the difunctional 1,2‐closo‐carborane C2B10H10{CH2OH}2and K2CO3in acetone have been investigated. These reactions led to the new spiro‐closo‐carboranylphosphazenes gem‐[N3P3Cl6−2n{(OCH2)2C2B10H10}n] (n=1 (1), 2 (2)) and the first fully carborane‐substituted phosphazene gem‐[N3P3{(OCH2)2C2B10H10}3] (3). A bridged product, non‐gem‐[N3P3Cl4{(OCH2)2C2B10H10}] (4), was also detected. The reaction of the well‐ known spiroderivatives [N3P3Cl2(O2C12H8)2] and [N3P3Cl4(O2C12H8)] with the same carborane‐diol and K2CO3in acetone gave the new compounds gem‐[N3P3(O2C12H8)3−n{(OCH2)2C2B10H10}n] (n=1 (5) or 2 (6), respectively), without signs of intra‐ or intermolecularly bridged species. Upon treatment with NEt3in acetone, compound 5was converted into the corresponding nido‐carboranylphosphazene. However, the reaction of gem‐[N3P3(O2C12H8)2{(OCH2)2C2B10H10}] (5) with NEt3in ethanol instead of acetone proceeded in a different manner to give the new compound (NHEt3)2[N3P3(O2C12H8)2(O){OCH2C2B9H10CH2OCH2CH3}] (7). For compounds with two 2,2′‐dioxybiphenyl units, gem‐[N3P3(O2C12H8)2{(OCH2)2C2B10H10}] (5), (NHEt3)[N3P3(O2C12H8)2{(OCH2)2C2B9H10}] (8), and (NHEt3)2[N3P3(O2C12H8)2(O){OCH2C2B9H10CH2OCH2CH3}] (7), a mixture of different stereoisomers may be expected. However, for 5and 7only the mesocompounds seem to be formed, with the same (R,S)‐configuration as in the precursor [N3P3Cl2(O2C12H8)2]. The reaction of 5to give 8seems to proceed with a change of configuration at one phosphorus center, giving a racemic mixture. The crystal structures of the nido‐carboranylphosphazenes 7and 8have been confirmed by X‐ray diffraction methods.

The treatment of NBu4[AuBr(C6F5)3] with NaSH affords the (hydrosulfido)gold(III) complex NBu4[Au(C6F5)3SH]. The latter compound reacts with [Au(C6F5)3OEt2] to give the dinuclear species NBu4[{Au(C6F5)3}2SH]. The isolobal analogy between H, AuPPh3, and AgPPh3 can be recognized in the complexes NBu4[{Au(C6F5)3}2S(MPPh3)] (M = Au, Ag) synthesized by reaction of NBu4[{Au(C6F5)3}2SH] with [Au(OClO3)(PPh3)] or [Ag(O3SCF3)(PPh3)] in the presence of Na2CO3. The structures of complexes NBu4[{Au(C6F5)3}2SR] (R = H, AuPPh3, AgPPh3) have been established by X-ray diffraction studies and show a trigonal-pyramidal geometry at sulfur with no short gold−gold or gold−silver interactions between the metallic centers.

The title compound, [Au2Cl2{Fe(C17H14P)2}], (I), contains the expected linear gold centres. The ferrocene moiety acts as a P,P′‐bridging ligand, wherein the Fe atom lies on an inversion centre. The P—Au—Cl angle is 177.56 (8)° and bond distances Au—P and Au—Cl are 2.2261 (18) and 2.2781 (18) Å, respectively. The structure is almost identical to that of the metal complex in (I)·2CH2Cl2[Canales, Gimeno, Jones, Laguna & Sarroca (1997). Inorg. Chem. 36, 5206–5211], but differs considerably from that in 3(I)·2CHCl3[Hill, Girard, McCabe, Johnson, Stupik, Zhang, Reiff & Eggleston (1989). Inorg. Chem. 28, 3529–3533], in that in the latter, the two independent mol­ecules are linked by a short Au⃛Au contact.

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ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

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ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.