4
Downloaded by MICHIGAN STATE UNIV on February 19, 2015 | http://pubs.acs.org Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0157.ch004
Organotin Phosphines, Arsines, Stibines, and Bismuthines: Starting Materials for New Catalysts HERBERT
SCHUMANN,
JOACHIM
HELD,
WOLF-W.
DU
MONT,
GISBERT
RODEWALD, and BERND WÖBKE Institut für Anorganische und Analytische Chemie der Technischen Universität Berlin, D-1000 Berlin, Germany
The preparation, properties, and reactions of organotin phosphines, arsines, stibines, and bismuthines are reviewed, and some newer results are described in detail. The title compounds react with some transition metal carbonyls to form organotin phosphine, arsine, stibine, and bismuthine substituted transition metal carbonyl complexes, which show unusual stability and may be useful homogeneous catalysts. The preparation and properties of some new systems for catalytical purposes are described: (1) organotin phosphines like (tertC H ) [CH3) SnCl]P react with metal carbonyls to form the corresponding complexes LM(CO) -1, which can be fixed on the surface of e.g., an aerosol by a strong Sn-O-Si bond; (2) pstyryl-substituted organotin phosphines can be synthesized. Transition metal complexes with these compounds as ligands can be copolymerized with olefins, yielding systematically synthesized polymeric organotin phosphine substituted transition metal carbonyl complexes. 4
9 2
2
n
I
n contrast to the organotin compounds in which tin is bound to a main-group element, like a halogen or chalcogen, organotin compounds with bonds between tin and a heavy element of the fifth main group of the periodic table are comparatively new. A patent (I ) in 1936 as well as several papers by Arbuzov et al., (2,3,4) and Malatesta (5) from 1947 to 1950 describe the synthesis of organotin phosphines, arsines, stibines, and bismuthines. However, it was shown later that these compounds did not contain direct bonds between tin and the group V element (6). The first real organotin phosphine was prepared in 57
In Organotin Compounds: New Chemistry and Applications; Zuckerman, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
58
ORGANOTIN COMPOUNDS:
NEW CHEMISTRY AND APPLICATIONS
1959 by Kuchen and Buchwald (7) and one year later by Bruker and co-workers (8): (C H ) SnBr + 2
5
NaP(C H )
3
6
3(CH )3SnBr +
3NaPH
Downloaded by MICHIGAN STATE UNIV on February 19, 2015 | http://pubs.acs.org Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0157.ch004
3
5
(C H > SnP(C H ) + NaBr
2
2
—
2
5
3
6
[(CH ) Sn] P + 3
3
5
(1)
2
3NaBr + 2 P H
3
(2)
3
In 1964 Jones and Lappert (9) prepared trimethyltin diphenylarsine, and Schumann and Schmidt (JO) isolated tris(triphenyltin)arsine as the first organotin arsenic compounds. In the same year Campbell, Fowles, and Nixon (JJ) and Schumann and Schmidt (JO) isolated the first antimony derivatives as well as the first bismuth compounds. Razuvaev et al. (12) then showed that the organotin bismuth derivatives could be prepared by the reaction of organotin hydride with triethylbismuth. (CH ) SnN(CH ) 3
3
3
+ HAs(C H )
2
6
5
—-
2
3 ( C H ) 3 S n L i -I- E C 1 — * 6
5
3
(CH ) SnAs(C H ) + (CH,) NH 3
3
6
[(0 Η )^η] Ε 6
5
3
5
2
2
+ LiCl
(3) (4)
Ε = A s , Sb, B i (CH ) SnCl + NaSb(C H ) — • (CH ) SnSb(C H ) + NaCl 3
3
6
5
2
3(C H ) SnH + Bi(C H ) 2
5
3
2
5
3
3
—
3
6
5
[(C,H ) Sn] Bi + 5
3
3
(5)
2
3C H 2
(6)
6
Analogous to the reaction of sulfur with tetraorganotin compounds (J3), we began in 1960 to prepare organotinphosphines by the reaction of tetraphenyltin with phosphorus in a sealed tube above 220° C. Triphenylphosphine and alloy-like tin phosphides were also formed (14). Although this reaction was not suitable for synthesizing specific organotin phosphines, we could isolate at 230° to 250° C, for example, cyclic trimeric diphenyltin phenylphosphine as well as small quantities of a tetrameric phenyltin phosphine having a cubane struc ture.
^ \ p /
C
S
n
\
/ C
p
6
H
CRH .
5
5
"SnC H . 6
5
I
I
eft -Snl
CfiH
C H 6
5
s
One method for preparing organotin phosphines is the reaction of organotin chlorides with lithium diphenylphosphide in tetrahydrofuran (THF) to form organotin phosphines (J5). The reaction of sodium diorganophosphide with organotin halides in liquid ammonia ( J5) is a better method. This reaction makes possible not only the synthesis of trialkyltin diorganophosphines, but also the isolation of diphenylbis(diphenylphosphino)tin. In addition this reaction proved its worth because it was possible to remove unreacted organotin halides from the
In Organotin Compounds: New Chemistry and Applications; Zuckerman, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1976.
Downloaded by MICHIGAN STATE UNIV on February 19, 2015 | http://pubs.acs.org Publication Date: June 1, 1976 | doi: 10.1021/ba-1976-0157.ch004
4.
S C H U M A N N
E T
AL.
59
New Catalysts
reaction mixture as their solid ammonia complexes. It is also possible to obtain organotin phosphines by removing alkali halides from alkali organotin compounds and organochlorophosphines in T M F but only in low yields (16). The reaction of organotin halides with phosphine or organophosphines in the presence of a base like triethylamine as a hydrogen halide acceptor is quite specific (J 7). The organotin amines are equally suitable as starting materials for synthesizing organotin phosphines. Trimethylbis(dimethylamino)tin, e.g., reacts not only with many other proton-active substances but also with diphenylphosphine or d i (terf-butyl)phosphine with the liberation of dimethylamine (18); trimethylsilylphosphines react with organotin chlorides and eliminate trimethylchlorosilane to form organotin phosphines (19). Trimethyltin chloride reacts with PCI3 or organochlorophosphines and magnesium in hexamethylphosphoramide to form organotin phosphines in high yields (20). The same methods could be used to synthesize organotin arsines, stibines, or bismuthines (21,22).
^ S n — C I
+ L i —
-^Sn—Li
+
CI
-^Sn—Cl
+
H—PC^
+
H — P ^
^ S n — C I Sn(C H ) 6
-^Sn—NR
2
y
