CHAPTER 12 • "9Sn Mtissbauer Spectroscopy Studies: Organotin(lV) Salts and Complexes
231
Table 12.1. 119Sn Mossbauer parameters of tributyltin(IV) and triphenyltin(IV) derivatives, interacted
with estuarine sediments'
Compound
t,e
!J.E',e
Interacted with sediments d
(mm s-') (mm s-') Anoxic d
Oxic d
t,d(mms-') !J.E',d(mms-') t,d(mms-') !J.E',d(mms-')
nBu3SnF
1.34
3.63
1.47-1.55
3.34-3.63
1.43-1.57
3.26-3.55
nBu3SnCI
1.56
3.43
1.29-1.49
1.65-3.25
1.47-1.54
3.42-3.56
nBu3Sn(02CCH3) 1.46
3.51
1.37-1.53
1.62-3.40
1.40-1.53
3.26-4.02
("Bu 3 Sn)p
1.11
1.55
1.29-1.50
1.58-2.90
1.35-1.50
2.20-3.54
("Bu 3 Sn)2S
1.49
1.71
1.27-1.44
1.66-3.26
1.21-1.45
1.63-3.21
("Bu 3 Sn)2S04
1.12
3.56
1.36-1.51
3.17-3.50
1.38-1.65
3.15-3.51
("Bu 3 Sn)2C03
1.46
3.30
1.34-1.48
1.64-3.16
1.35 e
3.28 e
Ph 3 SnF
1.36
3.62
1.22-1.36
2.99-3.62
1.21-1.30
3.09-3.63
Ph 3 SnCl
1.35
2.52
1.14-1.28
2.43-2.79
1.13-1.25
2.50-2.77
Ph 3 Sn(02CCH3) 1.29
3.31
1.12-1.21
2.63-2.76
1.04-1.15
2.51-2.76
Ph 3 SnOH
1.23
2.95
1.12-1.22
2.66-2.81
1.10-1.17
2.71-2.80
a Eng et al. 1986; May et al. 1994; Lucero et al. 1992; Whalen et al. 1993.
b 0= isomer shift with respect to BaSn0 3 ;!J.E = nuclear quadrupole splitting; T = 80 K.
C Data for solid state samples of the organotin(lV) salts employed in the interaction with sediments.
d See text. Ranges of 0 and !J.E measured for compounds interacted with sediments from series of
estuarine and marine sites. Neutral or basic pH was detected in suspensions of the anoxic sediments
investigated (in artificial seawater, at room temperature, without added organotins) unless otherwise
stated. See Refs. in note o.
e Data reported for one site. See May et al. 1994.
iii. nBu3SnOH and (nBu3SnhO show analogous interactions with oxic sediments, while,
when spiked to anoxic sediments, the oxide forms different compounds in samples
taken from given sites (Eng et al. 1986; May et al. 1994).
iv. (nBu3SnhS and (nBu3SnhC03 are converted to other derivatives when spiked to both
type of sediments (May et al. 1994).
v. Ph3SnOH and Ph3Sn(02CCH3) are probably converted to Ph3Sn+, which possibly
binds to both oxic and anoxic sediments; Ph 3 SnCI and Ph 3 SnF spike unaltered (Lucero
et al. 1992).
12.3
Interaction of Organotin(lV) Compounds with Biological Systems
The structures of tin bonding environment, calculated by the point-charge model treatment of the 119Sn parameter nuclear quadrupole splitting, have been reported for
RzSn(IV) and R 3 Sn(IV) (R = Alkyl, Aryl) derivatives interacted with human whole
erythrocytes, erythrocyte membranes, ghost cells, cytoplasm, as well as with rat liver
mitochondria and the mitochondrial membrane; data concerning systems organotin(IV)-cells, and cell walls, of the fungus Ceratocystis ulmi, are also given. Diorganotins
exhibit possible (distorted) trans-R2 octahedral configurations, as well as trigonal
231
Table 12.1. 119Sn Mossbauer parameters of tributyltin(IV) and triphenyltin(IV) derivatives, interacted
with estuarine sediments'
Compound
t,e
!J.E',e
Interacted with sediments d
(mm s-') (mm s-') Anoxic d
Oxic d
t,d(mms-') !J.E',d(mms-') t,d(mms-') !J.E',d(mms-')
nBu3SnF
1.34
3.63
1.47-1.55
3.34-3.63
1.43-1.57
3.26-3.55
nBu3SnCI
1.56
3.43
1.29-1.49
1.65-3.25
1.47-1.54
3.42-3.56
nBu3Sn(02CCH3) 1.46
3.51
1.37-1.53
1.62-3.40
1.40-1.53
3.26-4.02
("Bu 3 Sn)p
1.11
1.55
1.29-1.50
1.58-2.90
1.35-1.50
2.20-3.54
("Bu 3 Sn)2S
1.49
1.71
1.27-1.44
1.66-3.26
1.21-1.45
1.63-3.21
("Bu 3 Sn)2S04
1.12
3.56
1.36-1.51
3.17-3.50
1.38-1.65
3.15-3.51
("Bu 3 Sn)2C03
1.46
3.30
1.34-1.48
1.64-3.16
1.35 e
3.28 e
Ph 3 SnF
1.36
3.62
1.22-1.36
2.99-3.62
1.21-1.30
3.09-3.63
Ph 3 SnCl
1.35
2.52
1.14-1.28
2.43-2.79
1.13-1.25
2.50-2.77
Ph 3 Sn(02CCH3) 1.29
3.31
1.12-1.21
2.63-2.76
1.04-1.15
2.51-2.76
Ph 3 SnOH
1.23
2.95
1.12-1.22
2.66-2.81
1.10-1.17
2.71-2.80
a Eng et al. 1986; May et al. 1994; Lucero et al. 1992; Whalen et al. 1993.
b 0= isomer shift with respect to BaSn0 3 ;!J.E = nuclear quadrupole splitting; T = 80 K.
C Data for solid state samples of the organotin(lV) salts employed in the interaction with sediments.
d See text. Ranges of 0 and !J.E measured for compounds interacted with sediments from series of
estuarine and marine sites. Neutral or basic pH was detected in suspensions of the anoxic sediments
investigated (in artificial seawater, at room temperature, without added organotins) unless otherwise
stated. See Refs. in note o.
e Data reported for one site. See May et al. 1994.
iii. nBu3SnOH and (nBu3SnhO show analogous interactions with oxic sediments, while,
when spiked to anoxic sediments, the oxide forms different compounds in samples
taken from given sites (Eng et al. 1986; May et al. 1994).
iv. (nBu3SnhS and (nBu3SnhC03 are converted to other derivatives when spiked to both
type of sediments (May et al. 1994).
v. Ph3SnOH and Ph3Sn(02CCH3) are probably converted to Ph3Sn+, which possibly
binds to both oxic and anoxic sediments; Ph 3 SnCI and Ph 3 SnF spike unaltered (Lucero
et al. 1992).
12.3
Interaction of Organotin(lV) Compounds with Biological Systems
The structures of tin bonding environment, calculated by the point-charge model treatment of the 119Sn parameter nuclear quadrupole splitting, have been reported for
RzSn(IV) and R 3 Sn(IV) (R = Alkyl, Aryl) derivatives interacted with human whole
erythrocytes, erythrocyte membranes, ghost cells, cytoplasm, as well as with rat liver
mitochondria and the mitochondrial membrane; data concerning systems organotin(IV)-cells, and cell walls, of the fungus Ceratocystis ulmi, are also given. Diorganotins
exhibit possible (distorted) trans-R2 octahedral configurations, as well as trigonal